CN101796106A - Insulating sheet and multilayer structure - Google Patents

Insulating sheet and multilayer structure Download PDF

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Publication number
CN101796106A
CN101796106A CN200880105868A CN200880105868A CN101796106A CN 101796106 A CN101796106 A CN 101796106A CN 200880105868 A CN200880105868 A CN 200880105868A CN 200880105868 A CN200880105868 A CN 200880105868A CN 101796106 A CN101796106 A CN 101796106A
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China
Prior art keywords
insulating trip
filler
mentioned
skeleton
weight
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CN200880105868A
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Chinese (zh)
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CN101796106B (en
Inventor
前中宽
日下康成
青山卓司
樋口勋夫
中岛大辅
渡边贵志
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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Priority claimed from JP2007230482A external-priority patent/JP4922108B2/en
Priority claimed from JP2007329140A external-priority patent/JP2009149770A/en
Priority claimed from JP2008076347A external-priority patent/JP4922220B2/en
Priority claimed from JP2008078796A external-priority patent/JP2009231249A/en
Priority claimed from JP2008078797A external-priority patent/JP5150326B2/en
Application filed by Sekisui Chemical Co Ltd filed Critical Sekisui Chemical Co Ltd
Priority claimed from PCT/JP2008/065763 external-priority patent/WO2009031536A1/en
Publication of CN101796106A publication Critical patent/CN101796106A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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    • C08G59/508—Amines heterocyclic containing only nitrogen as a heteroatom having three nitrogen atoms in the ring
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    • H—ELECTRICITY
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Laminated Bodies (AREA)
  • Insulating Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Disclosed is an insulating sheet which is used for bonding a heat conductor having a thermal conductivity of not less than 10 W/m.K to an electrically conductive layer. This insulating sheet has excellent handling properties in an uncured state, and a cured product of this insulating sheet is improved in adhesiveness, heat resistance, dielectric breakdown characteristics and thermal conductivity. Specifically disclosed is an insulating sheet used for bonding a heat conductor having a thermal conductivity of not less than 10 W/m.K to an electrically conductive layer, which sheet contains (A) a polymer having an aromatic skeleton and a weight average molecular weight of not less than 10,000, (B) a monomer composed of at least one of (B1) an epoxy monomer having an aromatic skeleton and a weight average molecular weight of not more than 600 and (B2) an oxethane monomer, (C) a curing agent composed of a phenol resin, an acid anhydride having an aromatic skeleton or an alicyclic skeleton, a hydrogenated product of such an acid anhydride or a modified product of such an acid anhydride, and (D) a filler. This insulating sheet has a glass transition temperature Tg in an uncured state of not more than 25 DEG C.

Description

Insulating trip and laminate structures
Technical field
The present invention relates to a kind of insulating trip, this insulating trip is used for the heat conductor of thermal conductivity more than 10W/mK is bonded in conductive layer, particularly, the present invention relates to operability excellence under its uncured state and can improve the insulating trip of cementability, thermotolerance, puncture of insulation characteristic and thermal conductivity of cured article and the laminate structures that has used this insulating trip.
Background technology
In recent years, the miniaturization of electronics and high performance are developed.Meanwhile, the packing density of electronic unit improves thereupon, thereby necessity that the heat that produced by electronic unit is shed is more and more higher.Particularly in power-equipment purposes such as electromobile,, therefore be easy to generate high calorie owing to will apply high-voltage, big electric current.Necessity that this high calorie is effectively shed is more and more higher.
As heat dissipating method, what extensively adopt is will have high exothermicity and thermal conductivity to be bonded in method on the heat releasing source at the heat conductors such as aluminium more than the 10W/mK.Wherein, for this heat conductor is bonded on the heat releasing source, use insulation adhesives with insulativity.For the insulation adhesives, be strict with it and have high thermal conductivity coefficient.
As an example of above-mentioned insulation adhesives, a kind of insulation adhesive sheet being disclosed in the following patent documentation 1: the adhesive composite that contains Resins, epoxy, hardener for epoxy resin, curing catalyst, elastomerics and inorganic filler is contained be immersed in the woven fiber glass and the insulation adhesive sheet that obtains.According to the record in the patent documentation 1, in above-mentioned adhesive composite, the content of inorganic filling material is preferably in 3～50 quality % scopes.
Also known have an insulation adhesives that does not use woven fiber glass.For example, a kind of insulating adhesive that comprises bisphenol A type epoxy resin, phenoxy resin, novolac resin, 1-cyano ethyl-2-phenylimidazole, γ-Huan Yangbingyangbingjisanjiayangjiguiwan and aluminum oxide is disclosed in the embodiment of following patent documentation 2.In this patent documentation 2,, tertiary amine, acid anhydrides, imidazolium compounds, polyphenol resin and blocked isocyanate (マ ス Network イ ソ シ ア ネ one ト) etc. have been enumerated as curing agent for epoxy resin.
In addition, a kind of caking agent is disclosed in following patent documentation 3, in this caking agent, the content of the inorganic powder A of median size 0.1～0.9 μ m in 15～35 weight % scopes, the content of the inorganic powder B of median size 2.0～6.0 μ m in 0～40 weight % scope, the content of the inorganic powder C of median size 10.0～30.0 μ m is in 40～80 weight % scopes.The thermal conductivity of this caking agent is higher.And, owing to wherein contain the above-mentioned specific inorganic powder of the electrical insulating property excellence of above-mentioned specified quantitative, and therefore, the exothermicity height of this caking agent.
Disclose a kind of insulation adhesive sheet in the following patent documentation 4, contained in this insulation adhesive sheet: weight-average molecular weight more than 100,000 and contain epoxide group acrylic rubber, Resins, epoxy, curing agent for epoxy resin, curing catalyst, with epoxy resin compatibility and weight-average molecular weight at the high molecular weight resin 30,000 or more, reach mineral filler.With regard to its heat bonding temperature, the MV minium viscosity of the above-mentioned insulation adhesive sheet that employing capillary rheometer method is measured is in 100～2000Pas scope.
Patent documentation 1: TOHKEMY 2006-342238 communique
Patent documentation 2: Japanese kokai publication hei 8-332696 communique
Patent documentation 3: No. 2520988 communique of Japanese Patent
Patent documentation 4: No. 3498537 communique of Japanese Patent
Summary of the invention
In patent documentation 1, in the insulation adhesive sheet of record,, use woven fiber glass in order to improve operability.When using woven fiber glass, be difficult for carrying out filming, and in various processing such as laser processing, stamping-out processing or boring processing, have difficulties.In addition, it is lower to comprise the cured article thermal conductivity of insulation adhesive sheet of woven fiber glass.For this reason, possibly can't obtain sufficient exothermicity.In addition, owing to be adhesive composite to be contained be immersed in the woven fiber glass, therefore must prepare special impregnation equipment.
In patent documentation 2 in the insulating adhesive of record, owing to do not use woven fiber glass, therefore the above-mentioned variety of issue of enumerating can not take place.Yet under its uncured state, this insulating adhesive itself is not the sheet material with shape-holding property (independence), so the operability of this insulating adhesive is lower.
As the caking agent of record in the patent documentation 3, may exist the thermal conductivity of cured article of caking agent low, filler takes place locally to assemble, cause the cementability of the cured article of caking agent to reduce problem.The low problem of insulativity that also may have in addition, the cured article of caking agent.
The thermal conductivity of the cured article of the insulation adhesive sheet of record is lower in the patent documentation 4.Therefore possibly can't obtain sufficient exothermicity.
The object of the present invention is to provide a kind of insulating trip and used the laminate structures of this insulating trip, described insulating trip is used for the heat conductor of thermal conductivity more than 10W/mK is bonded in conductive layer, have excellent operation under its its uncured state, and the cementability of cured article, thermotolerance, puncture of insulation characteristic and thermal conductivity are improved.
The invention provides a kind of insulating trip, it is used for the heat conductor of thermal conductivity more than 10W/mK is bonded in conductive layer, and wherein, this insulating trip contains: polymkeric substance (A), and its weight-average molecular weight is more than 10,000 and have an aromatic series skeleton; At least a monomer (B) in epoxy monomer (B1) and the oxetane monomer (B2), the weight-average molecular weight of described epoxy monomer (B1) is below 600 and have an aromatic series skeleton, and the weight-average molecular weight of described oxetane monomer (B2) is below 600 and have an aromatic series skeleton; Solidifying agent (C), this solidifying agent (C) is for resol or have the aromatic series skeleton or the acid anhydrides of ester ring type skeleton, the hydrogenation thing of this acid anhydrides or the modifier of this acid anhydrides; Filler (D), wherein, comprising above-mentioned polymkeric substance (A), among all resins composition total amount 100 weight % in the insulating trip of above-mentioned monomer (B) and above-mentioned solidifying agent (C), the content of described polymkeric substance (A) is in 20～60 weight % scopes, the content of described monomer (B) is in 10～60 weight % scopes, and the total content of described polymkeric substance (A) and described monomer (B) is lower than 100 weight %, the glass transition temperature Tg of this insulating trip under its uncured state is below 25 ℃, after insulating trip solidified, the breakdown voltage of the cured article of insulating trip was more than 30kV/mm.
Above-mentioned polymkeric substance (A) is preferably phenoxy resin.When using phenoxy resin, the thermotolerance of the cured article of insulating trip can further improve.In addition, the glass transition temperature Tg of above-mentioned phenoxy resin is preferably more than 95 ℃.At this moment, the thermal degradation when of resin is able to further inhibition.
Above-mentioned solidifying agent (C) is preferably: have the acid anhydrides of greasiness ring type skeleton, the hydrogenation thing of this acid anhydrides or the modifier of this acid anhydrides, perhaps the acid anhydrides with ester ring type skeleton, the hydrogenation thing of this acid anhydrides or the modifier of this acid anhydrides that obtain through addition reaction of terpene compound and maleic anhydride.In addition, the acid anhydrides of arbitrary chemical formulation in the more preferably following formula of above-mentioned solidifying agent (C) (1)～(3).When using these preferred solidifying agent (C), the flexibility of insulating trip, wet fastness or cementability can further improve.
[Chemical formula 1]
Figure GPA00001045404100031
[Chemical formula 2]
Figure GPA00001045404100041
[chemical formula 3]
In above-mentioned formula (3), R1 and R2 represent the alkyl of hydrogen, hydroxyl or carbonatoms 1～5 respectively.
Above-mentioned solidifying agent (C) is preferably the resol with trimeric cyanamide skeleton or triazine skeleton or has allylic resol.When using this preferred solidifying agent (C), the flexibility of the cured article of insulating trip, flame retardant properties access further raising.
In a certain specific implementations of insulating trip of the present invention, described filler (D) contains the ball filler (D1) of median size 0.1～0.5 μ m, the ball filler (D2) of median size 2～6 μ m, the ball filler (D3) of median size 10～40 μ m, in the described filler (D) of 100 volume %, the content of described ball filler (D1) is in 5～30 volume % scopes, in content 20～60 volume % scopes of described ball filler (D2), the content of described ball filler (D3) is in 20～60 volume % scopes, and described ball filler (D1), the total content of described ball filler (D2) and described ball filler (D3) is no more than 100 volume %.
In another embodiment of insulating trip of the present invention, contained filler (D) is the filler (D4) through pulverize of median size below 12 μ m.
Above-mentioned filler (D) is preferably at least a kind that is selected from aluminum oxide, boron nitride, aluminium nitride, silicon nitride, silicon carbide, zinc oxide and the magnesium oxide.When using this filler (D), the exothermicity of the cured article of insulating trip can further improve.
In another embodiment of insulating trip of the present invention, also contain dispersion agent (F) in the described insulating trip, described dispersion agent (F) has the functional group that comprises the hydrogen atom that can form hydrogen bond.When using this dispersion agent (F), the thermal conductivity of the cured article of insulating trip and puncture of insulation characteristic can further improve.
In another embodiment of insulating trip of the present invention, also contain rubber grain (E) in the described insulating trip.When using rubber grain (E), the flexibility of the cured article of insulating trip and stress relaxation ability enough further improve.As rubber grain (E), preferably use silicone rubber particles.When using silicone rubber particles, the stress relaxation ability of the cured article of insulating trip enough further improves.
In another embodiment of insulating trip of the present invention, in whole skeletons 100 weight % of described polymkeric substance (A), the content of aromatic series skeleton is in 30～80 weight % scopes.
Preferably has polycycle aromatic series skeleton in the main chain of above-mentioned polymkeric substance (A).At this moment, the thermotolerance of the cured article of insulating trip can further improve.
Insulating trip of the present invention does not preferably contain woven fiber glass.Even insulating trip of the present invention does not contain woven fiber glass, it also has excellent operation under its uncured state.
In another embodiment of insulating trip of the present invention, the insulating trip of its uncured state in the bending elastic modulus under 25 ℃ in 10～1000MPa scope, and after insulating trip solidifies, the cured article of insulating trip in the bending elastic modulus under 25 ℃ in 100～50000MPa scope; Use its uncured state insulating trip that rotary-type Measurement of Dynamic Viscoelasticity device measures at the tan δ under 25 ℃ in 0.1～1.0 scope, and, when 25 ℃ were warming up to 250 ℃, the maximum value of the tan δ of insulating trip was in 1.0～5.0 scopes at the insulating trip that makes its uncured state.
In another embodiment of insulating trip of the present invention, the reactivity of described insulating trip under its uncured state is below 10%.
Laminate structures of the present invention possesses: thermal conductivity the heat conductor more than the 10W/mK, be laminated to the insulation layer on the one side at least of above-mentioned heat conductor and be laminated to above-mentioned insulation layer with lamination the opposite conductive layer on simultaneously of the face of above-mentioned heat conductor is arranged, wherein, the insulation layer of described insulation layer by insulating trip with formation of the present invention is solidified to form.
In laminate structures of the present invention, described heat conductor is preferably metal.
The effect of invention
Insulating trip of the present invention is owing to contain the above-mentioned polymkeric substance (A) of above-mentioned specified quantitative, above-mentioned monomer (B), above-mentioned solidifying agent (C) and above-mentioned filler (D), glass transition temperature Tg under its uncured state below 25 ℃ and the breakdown voltage of cured article more than 30kV/mm, therefore, the cementability of the operability of the insulating trip of its uncured state, insulating trip cured article, thermotolerance, puncture of insulation characteristic and thermal conductivity all can reach high level.In addition, because the breakdown voltage of the cured article of insulating trip is more than 30kV/mm, therefore suitable big current applications such as power-equipment, vehicle-mounted or great power LED that this insulating trip is used for.
Laminate structures of the present invention is the laminate structures that is situated between and is formed by the upper strata pressure conductive layer of one side at least of the heat conductor of insulation layer more than thermal conductivity 10W/mK, and this insulation layer is by the insulating trip with formation of the present invention is solidified to form, therefore, the heat that comes from the conductive layer side is easy to be situated between and is conducted to above-mentioned heat conductor by insulation layer.Thereby can realize effective heat radiation by this heat conductor.
Description of drawings
Fig. 1 schematically shows the laminate structures in the one embodiment of the present invention for part intercepts front cross-sectional view.
Nomenclature
1... laminate structures
2... conductive layer
2a... surface
3... insulation layer
4... heat conductor
The embodiment of invention
Below, the present invention is specifically described.
Discoveries such as the present application people, by taking following composition, and make its uncured state insulating trip glass transition temperature Tg below 25 ℃, the breakdown voltage of the cured article of insulating trip is more than 30kV/mm, the operability of its uncured state insulating trip can be improved, and cementability, thermotolerance, puncture of insulation characteristic and the thermal conductivity of the cured article of insulating trip can be improved.Wherein, described composition is to contain with above-mentioned specified quantitative: polymkeric substance (A), and its weight-average molecular weight is more than 10,000 and have an aromatic series skeleton; At least a monomer (B) in epoxy monomer (B1) and the oxetane monomer (B2), the weight-average molecular weight of described epoxy monomer (B1) is below 600 and have an aromatic series skeleton, and the weight-average molecular weight of described oxetane monomer (B2) is below 600 and have an aromatic series skeleton; Solidifying agent (C), this solidifying agent are resol or have the aromatic series skeleton or the acid anhydrides of ester ring type skeleton, the hydrogenation thing of this acid anhydrides or the modifier of this acid anhydrides; And filler (D).
Insulating trip of the present invention contains: polymkeric substance (A), and its weight-average molecular weight is more than 10,000 and have an aromatic series skeleton; At least a monomer (B) in epoxy monomer (B1) and the oxetane monomer (B2), the weight-average molecular weight of described epoxy monomer (B1) is below 600 and have an aromatic series skeleton, and the weight-average molecular weight of described oxetane monomer (B2) is below 600 and have an aromatic series skeleton; Solidifying agent (C), this solidifying agent are resol or have the aromatic series skeleton or the acid anhydrides of ester ring type skeleton, the hydrogenation thing of this acid anhydrides or the modifier of this acid anhydrides; And filler (D).
(polymkeric substance (A))
Contained above-mentioned polymkeric substance (A) in the insulating trip of the present invention is not as long as the weight-average molecular weight with aromatic series skeleton and this polymkeric substance more than 10,000, then has particular restriction.Polymkeric substance (A) may be used alone, or two or more kinds may be used in combination.
Polymkeric substance (A) can have the aromatic series skeleton so long as have the aromatic series skeleton get final product in its whole polymkeric substance in main chain backbone, also can have the aromatic series skeleton in side chain.Polymkeric substance (A) preferably has the structure of aromatic series skeleton in the main chain backbone.At this moment, the thermotolerance of the cured article of insulating trip can further improve.Polymkeric substance (A) preferably has the structure of polycycle aromatic series skeleton in the main chain.At this moment, the thermotolerance of the cured article of insulating trip can further improve.
There is no particular restriction for above-mentioned aromatic series skeleton.As the specific examples of above-mentioned aromatic series skeleton, can enumerate naphthalene skeleton, fluorene skeleton, biphenyl backbone, anthracene skeleton, pyrene skeleton, xanthene skeleton, diamantane skeleton or bisphenol A-type skeleton etc.Wherein, preferred biphenyl backbone or fluorene skeleton.At this moment, the thermotolerance of the cured article of insulating trip can further improve.
As above-mentioned polymkeric substance (A), can use thermoplastic resin or thermosetting resin etc.
There is no particular restriction for above-mentioned thermoplastic resin and thermosetting resin.As above-mentioned thermoplastic resin and thermosetting resin, for example can enumerate: thermoplastic resins such as polyphenylene sulfide, polyarylester, polysulfones, polyethersulfone, polyether-ether-ketone, polyetherketone.In addition, as above-mentioned thermoplastic resin and thermosetting resin, reactant that can use thermoplastic polyimide, Thermocurable polyimide, benzoxazine or polybenzoxazole and benzoxazine etc. is called as heat-resistant resin group of special engineering plastics etc.Thermoplastic resin can use separately, also can will be used in combination more than 2 kinds.Thermosetting resin can use separately, also can will be used in combination more than 2 kinds.One of any in thermoplastic resin and the thermosetting resin can be used, also thermoplastic resin and thermosetting resin can be used in combination.
Above-mentioned polymkeric substance (A) is preferably styrenic polymer or phenoxy resin, more preferably phenoxy resin.At this moment, can prevent the cured article generation oxidative degradation of insulating trip, and thermotolerance is further improved.
As above-mentioned styrenic polymer, specifically can use the homopolymer of styrene monomer or the multipolymer of styrene monomer and acrylic monomer etc.Wherein, the styrenic polymer that preferably has vinylbenzene-glycidyl methacrylate structure.
As above-mentioned styrene monomer, for example can enumerate: vinylbenzene, o-methyl styrene, a vinyl toluene, p-methylstyrene, to methoxy styrene, to styryl phenyl, to chloro-styrene, to ethyl styrene, align butylstyrene, to t-butyl styrene, to positive hexyl phenenyl ethene, to n-octyl vinylbenzene, align nonyl benzene ethene, align decyl vinylbenzene, align dodecyl vinylbenzene, 2,4-dimethyl styrene or 3,4-dichlorostyrene etc.Above-mentioned styrene monomer may be used alone, or two or more kinds may be used in combination.
As aforesaid propylene acids monomer, for example can enumerate: vinylformic acid, methacrylic acid, methyl acrylate, ethyl propenoate, butyl acrylate, ethyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, N-Hexyl methacrylate, methacrylic acid-2-ethylhexyl, glycidyl methacrylate, the beta-hydroxy ethyl propenoate, gamma-amino vinylformic acid propyl group, the methacrylic acid stearyl, dimethylaminoethyl methacrylate, or diethyl aminoethyl methacrylate etc.Aforesaid propylene acids monomer may be used alone, or two or more kinds may be used in combination.
As above-mentioned phenoxy resin, particularly, for example be by the reaction of epihalohydrins and divalent phenolic compound resin or by the divalent epoxy compounds with the reaction of divalent phenolic compound must resin.
Above-mentioned phenoxy resin preferably has at least a kind of skeleton in the group of being selected from down: bisphenol A-type skeleton, Bisphenol F type skeleton, dihydroxyphenyl propane/F mixed type skeleton, naphthalene skeleton, fluorene skeleton, biphenyl backbone, anthracene skeleton, pyrene skeleton, xanthene skeleton, diamantane skeleton and dicyclopentadiene skeleton.Wherein, above-mentioned phenoxy resin more preferably has at least a kind of skeleton in the group of being selected from down: bisphenol A-type skeleton, Bisphenol F type skeleton, dihydroxyphenyl propane/F mixed type skeleton, naphthalene skeleton, fluorene skeleton and biphenyl backbone; Further preferably has at least a kind in fluorene skeleton and the biphenyl backbone.When use had the phenoxy resin of above-mentioned preferred skeleton, the thermotolerance of the cured article of insulating trip can further improve.
Has polycycle aromatic series skeleton in the preferred main chain of above-mentioned phenoxy resin.And above-mentioned phenoxy resin more preferably has at least a kind of skeleton in the skeleton of following formula (4)～(9) expression in the main chain.
[chemical formula 4]
Figure GPA00001045404100081
In the above-mentioned formula (4), R 1Can be mutually the same also can be different, represent the alkyl or the halogen atom of hydrogen atom, carbonatoms 1～10, X 1For the divalent alkyl of singly-bound, carbonatoms 1～7 ,-O-,-S-,-SO 2-or-CO-.
[chemical formula 5]
Figure GPA00001045404100091
In the above-mentioned formula (5), R 1aCan be mutually the same also can be different, represent the alkyl or the halogen atom of hydrogen atom, carbonatoms 1～10, R 2Be the alkyl or the halogen atom of hydrogen atom, carbonatoms 1～10, R 3Be the alkyl of hydrogen atom or carbonatoms 1～10, m is 0～5 integer.
[chemical formula 6]
Figure GPA00001045404100092
In the above-mentioned formula (6), R 1bCan be mutually the same also can be different, represent the alkyl or the halogen atom of hydrogen atom, carbonatoms 1～10, R 4Can be mutually the same also can be different, represent the alkyl or the halogen atom of hydrogen atom, carbonatoms 1～10,1 is 0～4 integer.
[chemical formula 7]
Figure GPA00001045404100093
[chemical formula 8]
Figure GPA00001045404100101
In the above-mentioned formula (8), R 5And R 6Be the alkyl or the halogen atom of hydrogen atom, carbonatoms 1～5, X 2For-SO 2-,-CH 2-,-C (CH 3) 2-or-O-, k is 0 or 1.
[chemical formula 9]
Figure GPA00001045404100102
As above-mentioned polymkeric substance (A), the preferred phenoxy resin that uses for example following formula (10) or following formula (11) expression.
[Chemical formula 1 0]
Figure GPA00001045404100103
In the above-mentioned formula (10), A 1Structure with any chemical formulation in above-mentioned formula (4)～(6), and in this structure, the structure of above-mentioned formula (4) expression is that the structure of 0～60 mole of %, above-mentioned formula (5) expression is that the structure that 5～95 moles of % and above-mentioned formula (6) are represented is 5～95 moles of %; A 2Be the group of hydrogen atom or above-mentioned formula (7) expression, n 1It in mean value 25～500 number.
[Chemical formula 1 1]
In the above-mentioned formula (11), A 3Structure with the expression of above-mentioned formula (8) or above-mentioned formula (9), n 2Value is at least more than 21.
The glass transition temperature Tg of above-mentioned polymkeric substance (A) is preferably in 60～200 ℃ of scopes, more preferably in 90～180 ℃ of scopes.If the Tg of polymkeric substance (A) is low excessively, then may cause resin generation thermal degradation when.If the Tg of polymkeric substance (A) is too high, then can cause the consistency variation between polymkeric substance (A) and other resin.Its result may cause that the thermotolerance of the cured article of the operability of insulating trip under its uncured state and insulating trip reduces.
When above-mentioned polymkeric substance (A) was phenoxy resin, the glass transition temperature Tg of phenoxy resin was preferably more than 95 ℃, more preferably more than 100 ℃.The second-order transition temperature of phenoxy resin further preferably in 110～200 ℃ of scopes, especially preferably in 110～180 ℃ of scopes.If the Tg of phenoxy resin is low excessively, then thermal degradation when may take place in resin.If the Tg of phenoxy resin is too high, then can cause the consistency variation between phenoxy resin and other resin.Its result may cause that the thermotolerance of the cured article of the operability of insulating trip and insulating trip reduces.
The weight-average molecular weight of above-mentioned polymkeric substance (A) is more than 10,000.The weight-average molecular weight of polymkeric substance (A) is preferably more than 30,000.The weight-average molecular weight of polymkeric substance (A) is more preferably 30,000～1, in 000,000 scope, further preferably 40,000～250, in 000 scope.If the weight-average molecular weight of polymkeric substance (A) is too small, then may cause insulating trip generation thermal degradation when.If the weight-average molecular weight of polymkeric substance (A) is excessive, then can cause the consistency variation between polymkeric substance (A) and other resin.Its result may cause that the thermotolerance of the cured article of the operability of insulating trip and insulating trip reduces.
In whole skeletons 100 weight % of above-mentioned polymkeric substance (A), the content of aromatic series skeleton is preferably in 30～80 weight % scopes.At this moment, under the interaction of electrons between the aromatic series skeleton,, the operability of its uncured state insulating trip is significantly improved even insulating trip also has shape-holding property under its uncured state.If the content of above-mentioned aromatic series skeleton is lower than 30 weight %, then may cause the operability of its uncured state insulating trip to reduce.Above-mentioned aromatic series skeleton is many more, and then the operability of its uncured state insulating trip is high more., if the content of above-mentioned aromatic series skeleton surpasses 80 weight %, then may cause insulating trip to become hard and crisp.In whole skeletons 100 weight % of above-mentioned polymkeric substance (A), the content of aromatic series skeleton is more preferably in 40～80 weight % scopes, further preferably in 50～70 weight % scopes.
In the total amount 100 weight % of all resins composition of the insulating trip that comprises above-mentioned polymkeric substance (A), above-mentioned monomer (B) and above-mentioned solidifying agent (C), the content of polymkeric substance (A) is in 20～60 weight % scopes.In the total amount 100 weight % of above-mentioned all resins composition, the content of polymkeric substance (A) is preferably in 30～50 weight % scopes.Preferred polymers (A) in above-mentioned scope and the total content of polymkeric substance (A) and monomer (B) be lower than 100 weight %.If the content of polymkeric substance (A) is very few, then may cause the operability of its uncured state insulating trip to reduce.If the content of polymkeric substance (A) is too much, then may cause filler (D) to be difficult for disperseing.Need to prove that described all resins composition refers to: polymkeric substance (A), epoxy monomer (B1), oxetane monomer (B2), solidifying agent (C) and as required and the summation of other resinous principle that adds.
(monomer (B))
Insulating trip of the present invention comprises at least a monomer (B) in epoxy monomer (B1) and the oxetane monomer (B2), the weight-average molecular weight of described epoxy monomer (B1) is below 600 and have an aromatic series skeleton, and the weight-average molecular weight of described oxetane monomer (B2) is below 600 and have an aromatic series skeleton.In insulating trip, as monomer (B), can only use epoxy monomer (B1), also can only use oxetane monomer (B2), can also use epoxy monomer (B1) and oxetane monomer (B2) the two.
Above-mentioned epoxy monomer (B1) if having the aromatic series skeleton and this monomeric weight-average molecular weight 600 with the next particular restriction that there is no.As the specific examples of above-mentioned epoxy monomer (B1), can enumerate: have the bis-phenol skeleton epoxy monomer, have the dicyclopentadiene skeleton epoxy monomer, have the naphthalene skeleton epoxy monomer, have the diamantane skeleton epoxy monomer, have fluorene skeleton epoxy monomer, have biphenyl backbone epoxy monomer, have two (glycidoxypropyl phenyl) methane skeleton epoxy monomer, have the xanthene skeleton epoxy monomer, have the epoxy monomer of anthracene skeleton or have epoxy monomer of pyrene skeleton etc.These epoxy monomers (B1) may be used alone, or two or more kinds may be used in combination.
As above-mentioned epoxy monomer with bis-phenol skeleton, can enumerate for example have bisphenol A-type, the epoxy monomer of the bis-phenol skeleton of Bisphenol F type or bisphenol S type etc.
As above-mentioned epoxy monomer, can enumerate bicyclopentadiene dioxide or have phenolic varnish epoxy monomer of dicyclopentadiene skeleton etc. with dicyclopentadiene skeleton.
As above-mentioned epoxy monomer with naphthalene skeleton, can enumerate: 1-glycidyl naphthalene, 2-glycidyl naphthalene, 1,2-diglycidyl naphthalene, 1,5-diglycidyl naphthalene, 1,6-diglycidyl naphthalene, 1,7-diglycidyl naphthalene, 2,7-diglycidyl naphthalene, triglycidyl group naphthalene or 1,2,5,6-four glycidyl group naphthalene etc.
As above-mentioned epoxy monomer, can enumerate with diamantane skeleton: 1, two (the 4-glycidoxypropyl phenyl) diamantane or 2 of 3-, two (4-glycidoxypropyl phenyl) diamantane of 2-etc.
As above-mentioned epoxy monomer with fluorene skeleton, can enumerate: 9, two (the 4-glycidoxypropyl phenyl) fluorenes of 9-, 9, two (4-glycidoxypropyl-3-aminomethyl phenyl) fluorenes of 9-, 9, two (4-glycidoxypropyl-3-chloro-phenyl-) fluorenes of 9-, 9, two (4-glycidoxypropyl-3-bromophenyl) fluorenes of 9-, 9, two (4-glycidoxypropyl-3-fluorophenyl) fluorenes of 9-, 9, two (4-glycidoxypropyl-3-p-methoxy-phenyl) fluorenes of 9-, 9, two (4-glycidoxypropyl-3, the 5-3,5-dimethylphenyl) fluorenes of 9-, 9, two (the 4-glycidoxypropyl-3 of 9-, the 5-dichlorophenyl) fluorenes, or 9, two (4-glycidoxypropyl-3,5-dibromo phenyl) fluorenes of 9-etc.
As above-mentioned epoxy monomer, can enumerate with biphenyl backbone: 4,4 '-diglycidyl biphenyl or 4,4 '-diglycidyl-3,3 ', 5,5 '-tetramethyl biphenyl etc.
As above-mentioned epoxy monomer with two (glycidoxypropyl phenyl) methane skeleton, can enumerate: 1,1 '-two (2,7-glycidoxypropyl naphthyl) methane, 1,8 '-two (2,7-glycidoxypropyl naphthyl) methane, 1,1 '-two (3,7-glycidoxypropyl naphthyl) methane, 1,8 '-two (3,7-glycidoxypropyl naphthyl) methane, 1,1 '-two (3,5-glycidoxypropyl naphthyl) methane, 1,8 '-two (3,5-glycidoxypropyl naphthyl) methane, 1,2 '-two (2,7-glycidoxypropyl naphthyl) methane, 1,2 '-two (3,7-glycidoxypropyl naphthyl) methane, or 1,2 '-two (3,5-glycidoxypropyl naphthyl) methane etc.
As above-mentioned epoxy monomer, can enumerate 1,3,4,5,6,8-hexamethyl-2,7-bisoxirane ylmethoxy-9-phenyl-9H-xanthene etc. with xanthene skeleton.
Above-mentioned oxetane monomer (B2) so long as weight-average molecular weight below 600 and the oxetane monomer with aromatic series skeleton then do not have particular restriction.Specific examples as above-mentioned oxetane monomer (B2), for example can enumerate: 4,4 '-two [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 1, two [(3-ethyl-3-oxetanyl) methyl] esters, 1 of 4-benzene dicarboxylic acid, two [(3-ethyl-3-oxetanyl) methoxymethyl] benzene of 4-or trimethylene oxide phenolic varnish etc.These oxetane monomers (B2) can use separately, also can will be used in combination more than 2 kinds.
The weight-average molecular weight of above-mentioned epoxy monomer (B1) and oxetane monomer (B2), be that the weight-average molecular weight of monomer (B) is below 600.The preferred lower limit of the weight-average molecular weight of monomer (B) is 200, preferred upper limit is 550.If the weight-average molecular weight of monomer (B) is too small, then may cause the volatility of monomer (B) too high, the operability of insulating trip reduces.If the weight-average molecular weight of monomer (B) is excessive, then may cause the become cementability of cured article of hard and crisp or insulating trip of insulating trip to reduce.
In the total amount 100 weight % of all resins composition of the insulating trip that comprises above-mentioned polymkeric substance (A), above-mentioned monomer (B), above-mentioned solidifying agent (C), the content of monomer (B) is in 10～60 weight % scopes.In the total amount 100 weight % of above-mentioned all resins composition, the content of monomer (B) is more preferably in 10～40 weight % scopes.Preferred monomers (B) in above-mentioned scope and the total content of polymkeric substance (A) and monomer (B) be lower than 100 weight %.If the content of monomer (B) is very few, then may cause the cementability of the cured article of insulating trip, thermotolerance to reduce.If the content of monomer (B) is too much, then may cause the flexibility of insulating trip to reduce.
(solidifying agent (C))
Above-mentioned solidifying agent (C) is for resol or have the aromatic series skeleton or the acid anhydrides of ester ring type skeleton, the hydrogenation thing of this acid anhydrides or the modifier of this acid anhydrides.By using this solidifying agent (C), can obtain the cured article that thermotolerance, wet fastness and electric rerum natura obtain well balanced insulating trip.Solidifying agent (C) may be used alone, or two or more kinds may be used in combination.
There is no particular restriction for above-mentioned resol.As the specific examples of above-mentioned resol, can enumerate: phenol phenolic varnish, o-Hydroxytoluene Novolac, p-cresol phenolic varnish, tert.-butyl phenol phenolic varnish, dicyclopentadiene cresols, poly-vinylphenol, bisphenol A-type phenolic varnish, xylylene modified novolac, perhydronaphthalene modified novolac, poly-(two o-hydroxy-phenyls) methane, poly-(two hydroxy phenyls) methane or poly-(two p-hydroxybenzenes) methane etc.Wherein, because have the resol of trimeric cyanamide skeleton, the flame retardant resistance that has the resol of triazine skeleton or have a cured article of flexibility that allylic resol can make insulating trip, insulating trip further improves, and is therefore preferred.
Commercially available prod as above-mentioned resol, can enumerate: MEH-8005, MEH-8010 and NEH-8015 (above bright the and company that changes into makes by Japan), YLH903 (manufacturing of japan epoxy resin company), LA-7052, LA-7054, LA-7751, LA-1356 and LA-3018-50P (above), and PS6313 and PS6492 (above) etc. by the manufacturing of the flourish chemical company of Japan group by the manufacturing of big Japanese ink company.
There is no particular restriction for the hydrogenation thing of the acid anhydrides with aromatic series skeleton, this acid anhydrides or the modifier of this acid anhydrides.As the hydrogenation thing of the acid anhydrides with aromatic series skeleton, this acid anhydrides or the modifier of this acid anhydrides, for example can enumerate: phenylethylene/maleic anhydride copolymer, benzophenone tetracarboxylic anhydride, pyromellitic acid acid anhydride, trimellitic acid 1,2-anhydride, 4,4 '-oxygen di-Tetra hydro Phthalic anhydride, phenylacetylene base Tetra hydro Phthalic anhydride, two (dehydration trimellitate) monoacetates of glycerine, ethylene glycol bis (dehydration trimellitate), methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride or trialkyl Tetra Hydro Phthalic Anhydride etc.Wherein, preferable methyl norbornene dicarboxylic anhydride or trialkyl Tetra Hydro Phthalic Anhydride.When using methyl norbornene dioic anhydride or trialkyl Tetra Hydro Phthalic Anhydride, can improve the water tolerance of the cured article of insulating trip.
As above-mentioned acid anhydrides with aromatic series skeleton, the commercially available prod of the hydrogenation thing of this acid anhydrides or the modifier of this acid anhydrides, can enumerate: SMA RESIN EF30, SMA RESIN EF40, SMA RESINEF60 and SMA RESIN EF80 (above) by the manufacturing of Sartomer Japan company, ODPA-M and PEPA (above) by the manufacturing of MANAC company, Rikacid MTA-10, Rikacid MTA-15, Rikacid TMTA, Rikacid TMEG-100, Rikacid TMEG-200, Rikacid TMEG-300, Rikacid TMEG-500, Rikacid TMEG-S, Rikacid TH, Rikacid HT-1A, RikacidHH, Rikacid MH-700, Rikacid MT-500, Rikacid DSDA and Rikacid TDA-100 (above make), and EPICLON B4400 by new Japanese physics and chemistry company, EPICLON B650, and EPICLON B570 (above by the manufacturing of big Japanese ink chemical company) etc.
In addition, having the acid anhydrides of ester ring type skeleton, the hydrogenation thing of this acid anhydrides or the modifier of this acid anhydrides is preferably: have the acid anhydrides with ester ring type skeleton, the hydrogenation thing of this acid anhydrides or the modifier of this acid anhydrides that acid anhydrides, terpene compound and the maleic anhydride of greasiness ring type skeleton obtain through addition reaction.At this moment, the flexibility of insulating trip, wet fastness or adhesiveproperties access further raising.In addition, have the acid anhydrides of ester ring type skeleton, the hydrogenation thing of this acid anhydrides or a modifier of this acid anhydrides, can also enumerate methyl norbornene dioic anhydride, have the acid anhydrides of dicyclopentadiene skeleton or the modifier of this acid anhydrides etc. as above-mentioned.
As the commercially available prod of the modifier of the hydrogenation thing of above-mentioned acid anhydrides with ester ring type skeleton, this acid anhydrides or this acid anhydrides, can enumerate Rikacid HNA and Rikacid HNA-100 (above make) and EPICURE YH306, EPICURE YH307, EPICURE YH308H and EPICURE YH309 (above make) etc. by japan epoxy resin company by new Japanese physics and chemistry company.
In addition, any represented acid anhydrides in the more preferably following formula of above-mentioned solidifying agent (C) (1)～(3).When using this preferred consolidation agent (C), the flexibility of insulating trip, wet fastness or adhesiveproperties access further raising.
[Chemical formula 1 2]
[Chemical formula 1 3]
Figure GPA00001045404100152
[Chemical formula 1 4]
Figure GPA00001045404100161
In the above-mentioned formula (3), R1 and R2 represent the alkyl of hydrogen, hydroxyl or carbonatoms 1～5 respectively.
For the rerum natura of curing speed, cured article etc. is adjusted, use curing catalyst when can also state solidifying agent in the use.
There is no particular restriction for described curing catalyst.As the specific examples of curing catalyst, for example can enumerate: Diazabicycloalkene classes such as tertiary amine, imidazoles, imidazolines, triazines, organophosphorus compound, quaternary phosphine salt or organic acid salt etc.In addition, as above-mentioned curing catalyst, can enumerate organometallic compound class, quaternary ammonium salt or metal halide.As above-mentioned organometallic compound class, can enumerate zinc octoate, stannous octoate, acetyl acetone aluminium complex etc.
As above-mentioned curing catalyst, can use dystectic imidazoles curing catalyst, dystectic decentralized potentiality curing catalyst, microcapsule-type potentiality curing catalyst, amine salt type potentiality curing catalyst or high temperature dissociative type and positively charged ion hot polymerization mould assembly potentiality curing catalyst etc.These curing catalysts can use separately, also can be used in combination more than 2 kinds.
As above-mentioned dystectic decentralized potentiality promotor, can enumerate dicyanamide or amine are added amine add-on type promotor that is formed in epoxy monomer etc. and obtains etc.As above-mentioned microcapsule-type potentiality promotor, can be set forth in imidazoles, Phosphorus or phosphine class promotor surface is coated with the microcapsule-type potentiality promotor of polymkeric substance.As above-mentioned high temperature dissociative type and positively charged ion hot polymerization mould assembly potentiality curing catalyst, can enumerate lewis acid or Bronsted hydrochlorate etc.
Above-mentioned curing catalyst is preferably dystectic imidazoles curing catalyst.When using dystectic imidazoles curing catalyst, can be easy to reaction system is controlled, and can be more easily the rerum natura of the cured article of the curing speed of insulating trip, insulating trip etc. be adjusted.Fusing point has excellent operation at the high-melting-point curing catalyst more than 100 ℃.Therefore, the fusing point of curing catalyst is preferably more than 100 ℃.
In the total amount 100 weight % of all resins composition of the insulating trip that comprises above-mentioned polymkeric substance (A), above-mentioned monomer (B), above-mentioned solidifying agent (C), the content of solidifying agent (C) preferably in 10～40 weight % scopes, more preferably in 12～25 weight % scopes.If the content of solidifying agent (C) is very few, then may be difficult to insulating trip is fully solidified.If the content of solidifying agent (C) is too much, then may produces and solidify irrelevant unnecessary solidifying agent or cause that cured article is crosslinked to carry out not exclusively.Thus, may cause the thermotolerance of the cured article of insulating trip, cementability fully to improve.
(filler (D))
Owing to contain filler (D) in the insulating trip of the present invention, therefore the thermal conductivity of the cured article of insulating trip is improved.Thus, can improve the exothermicity of the cured article of insulating trip.Filler (D) may be used alone, or two or more kinds may be used in combination.
(D) there is no particular restriction for filler.The thermal conductivity of filler (D) is preferably more than 30W/mK.As the filler (D) of thermal conductivity more than 30W/mK, can enumerate aluminum oxide, boron nitride, aluminium nitride, silicon nitride, silicon carbide, zinc oxide or magnesium oxide etc.
Filler (D) is preferably at least a kind that is selected from aluminum oxide, boron nitride, aluminium nitride, silicon nitride, silicon carbide, zinc oxide and the magnesium oxide.At this moment, the exothermicity of the cured article of insulating trip can further improve.In addition, filler (D) also is preferably at least a kind that is selected from aluminum oxide, boron nitride, aluminium nitride, silicon nitride, silicon carbide and the magnesium oxide.
Filler (D) more preferably is selected from least a kind in aluminum oxide, boron nitride, aluminium nitride, silicon nitride and the silicon carbide.At this moment, if use pKa low be the high dispersion agent of acidity as dispersion agent described later (F), then can suppress the dissolving of filler (D) in dispersion agent (F).
Filler (D) especially is preferably and is selected from least a in spherical alumina and the spherical aluminium nitride.During at least a in using spherical alumina and spherical aluminium nitride, can fill filler (D), therefore the exothermicity of the cured article of insulating trip is further improved with high-density.
The median size of filler (D) is preferably in 0.1～40 mu m range.If median size less than 0.1 μ m, then may be difficult to fill filler (D) with high-density.If median size surpasses 40 μ m, may cause that then the puncture of insulation characteristic of the cured article of insulating trip reduces.
Described " median size " is meant: by the median size that volume average particle sizes measure of spread result obtains, described volume average particle sizes measure of spread result utilizes laser diffraction formula particle size distribution device to measure.
In insulating trip 100 volume %, the content of filler (D) preferably in 40～90 volume % scopes, more preferably in 50～90 volume % scopes.The preferred lower limit of the combined amount of filler (D) is 65 volume %, and preferred upper limit is 85 volume %.If the content of filler (D) is very few, then possibly the exothermicity of the cured article of insulating trip is fully improved.If the content of filler (D) is too much, then may cause the flexibility of insulating trip, cementability significantly to reduce.
The ball filler (D2), and the ball filler (D3) of median size 10～40 μ m that preferably contain ball filler (D1), median size 2～6 μ m of median size 0.1～0.5 μ m in the filler (D).At this moment, in filler (D) 100 volume %, the content of preferred ball filler (D1) in 5～30 volume % scopes, the content of ball filler (D2) in 20～60 volume % scopes, the content of ball filler (D3) in 20～60 volume % scopes and the total content of ball filler (D1), ball filler (D2) and ball filler (D3) be no more than 100 volume %.
When the ball filler (D3) of ball filler (D2) that is used in combination the ball filler (D1) of small particle size, middle particle diameter with above-mentioned certain content and big particle diameter, the thermal conductivity of the cured article of insulating trip is further improved, and the cementability of cured article and puncture of insulation characteristic are further enhanced.
Ball filler (D1) if median size less than 0.1 μ m, then may cause the cementability of the cured article of the filling difficulty of filler (D) or insulating trip to reduce.
If the median size of ball filler (D1) surpasses the median size of 0.5 μ m or above-mentioned ball filler (D2) less than 2 μ m, then can cause the particle diameter of ball filler (D1) and ball filler (D2) too approaching, and then may be difficult to the fillibility that forms fine and close interstitital texture, can't fully guarantee filler (D).So, may cause that the thermal conductivity of the cured article of insulating trip reduces, or cause that the cementability and the insulativity reduction of the cured article of local gathering, insulating trip take place filler (D).
If the median size of ball filler (D2) surpasses the median size of 6 μ m or above-mentioned filler (D3) less than 10 μ m, then can cause ball filler (D2) too approaching, and then possibly can't fully guarantee the fillibility of filler (D) with the particle diameter of ball filler (D3).So, may cause that the thermal conductivity of the cured article of insulating trip reduces, or cause that filler (D) condenses, the cementability of the cured article of insulating trip and insulativity reduction.
If the median size of ball filler (D3) surpasses 40 μ m, then when the thickness of insulating trip is as thin as the 100 μ m left and right sides, may cause that the insulativity of the cured article of insulating trip significantly reduces.
Need to prove, in above-mentioned patent documentation 3, in the caking agent of record, cooperated 3 kinds of different inorganic powder A～C of particle diameter.; for example; when using median size to surpass 0.5 μ m and the inorganic powder below 0.9 μ m as above-mentioned inorganic powder A, because this inorganic powder A is too approaching with the particle diameter of the inorganic powder B of median size 2.0～6.0 μ m, therefore possibly can't fully be guaranteed the fillibility of inorganic powder.So, may cause that the thermal conductivity of the cured article of caking agent reduces, or cause filler generation localized agglomeration that the cementability of the cured article of caking agent and insulativity reduce.In addition, when the use level of the inorganic powder C of or median size 10～30 μ ms very few when the use level of the inorganic powder B of median size 2.0～6.0 μ m is too much, possibly can't fully guarantee the fillibility of inorganic filling material.So, may cause that the thermal conductivity of the cured article of caking agent reduces, or cause filler generation localized agglomeration that the cementability of the cured article of caking agent and insulativity reduce.
In addition, in above-mentioned patent documentation 3, in the caking agent of record, except inorganic powder A～C, also mixed other resinous principle kind, and the kind of these other resinous principles may cause the puncture of insulation characteristic of the cured article of caking agent, cementability to reduce.
If in filler (D), do not contain ball filler (D1), (D2) and (D3) respectively, then possibly can't fully guarantee the fillibility of filler (D) with above-mentioned volume ratio.So, may cause the thermal conductivity of the cured article of insulating trip to reduce.In addition, also may cause filler (D) cohesion, the cementability of the cured article of insulating trip and insulativity reduce.
It is spherical that above-mentioned ball filler (D1), (D2) reach (D3).The described spherical shape of length-to-diameter ratio in 1～2 scope that refer to.
When using ball filler (D1), (D2) and (D3) time, can also contain in the filler (D) with ball filler (D1), (D2) and reach (D3) different or non-other filler of globular of particle diameter.Preferably do not contain other above-mentioned filler in the insulating trip.For the situation that comprises above-mentioned other filler, in filler (D) 100 volume %, the ratio of contained above-mentioned other filler is below 5 volume %.
As the size-grade distribution of ball filler (D1), preferably below 2 μ m, minimum grain size is preferably more than 0.01 μ m for its maximum particle diameter.As the size-grade distribution of above-mentioned ball filler (D2), preferably below 40 μ m, minimum grain size is preferably more than 0.1 μ m for its maximum particle diameter.As the size-grade distribution of above-mentioned ball filler (D3), preferably below 60 μ m, minimum grain size is preferably more than 0.5 μ m for its maximum particle diameter.
When the size-grade distribution of contained whole fillers (D) is measured in to insulating trip, when when the little filler of particle diameter begins to measure the cumulative volume of filler (D), the cumulative volume at particle diameter 0.1 μ m place is preferably in 0～5% scope, the cumulative volume % at particle diameter 0.5 μ m place is preferably in 1～10% scope, the cumulative volume % at particle diameter 2 μ m places is preferably in 2～20% scopes, the cumulative volume % at particle diameter 6 μ m places is preferably in 20～50% scopes, the cumulative volume % at particle diameter 10 μ m places is preferably in 30～80% scopes, the cumulative volume % at particle diameter 40 μ m places is preferably in 80～100% scopes.
Described " size-grade distribution " refers to the volume average particle sizes of measuring with laser diffraction formula particle size distribution device and distributes.
Above-mentioned ball filler (D1), (D2) and principal constituent (D3) are preferably identical.The dispersion inequality of the filler (D) that causes because of difference of specific gravity etc. be difficult for to take place at this moment.
Filler (D) is preferably the following filler (D4) through pulverizing of median size 12 μ m.May be used alone, or two or more kinds may be used in combination through the filler of pulverizing (D4).
Can obtain by utilizing single shaft pulverizer, twin shaft pulverizer, hammer mill or ball mill etc. that block inorganic substance are pulverized through the filler of pulverizing (D4).When using, obtain easily that filler (D) in the insulating trip takes place to build bridge or effective approaching structure through the filler (D4) pulverized.Thus, the thermal conductivity of the cured article of insulating trip is further improved.In addition, compare with the filler of routine, more cheap usually through the filler of pulverizing (D4).So, can be by using the cost that reduces insulating trip through the filler of pulverizing (D4).
The median size of the filler (D4) that process is pulverized is below 12 μ m.If median size surpasses 12 μ m, the filler (D4) through pulverizing is dispersed in the insulating trip with high-density, and then causes that the puncture of insulation characteristic of the cured article of insulating trip reduces.The preferred upper limit of the median size of the filler (D4) that process is pulverized is 10 μ m, and preferred lower limit is 1 μ m.If the median size of filler (D4) is too small, then may be difficult to carrying out highdensity filling through the filler of pulverizing (D4).
There is no particular restriction for the length-to-diameter ratio of passing through the filler of pulverizing (D4).The length-to-diameter ratio of the filler (D4) that process is pulverized is preferably in 1.5～20 scopes.It is higher that length-to-diameter ratio is lower than the price of 1.5 filler, so, can cause the cost of insulating trip to increase.If above-mentioned length-to-diameter ratio surpasses 20, then may cause the filling of the filler (D4) of process pulverizing to become difficult.
The length-to-diameter ratio of the filler (D4) that process is pulverized can be obtained by following method: for example, use digital picture analysis mode particle size distribution device (trade(brand)name: FPA, Japan Rufuto company makes), crushed face to filler is measured, thereby asks the length-to-diameter ratio of calculating through the filler of pulverizing (D4).
Be preferably at least a kind that is selected from aluminum oxide, boron nitride, aluminium nitride, silicon nitride and the silicon carbide through the filler of pulverizing (D4).But when using these preferably to pass through the filler of pulverizing (D4), the exothermicity of the cured article of insulating trip is further improved.
(dispersion agent (F))
Insulating trip of the present invention preferably further contains dispersion agent (F), and this dispersion agent (F) has the functional group that comprises the hydrogen atom that can form hydrogen bond.When comprising above-mentioned dispersion agent (F), the thermal conductivity and the puncture of insulation characteristic of the cured article of insulating trip are further improved.Dispersion agent (F) can use separately, also can be used in combination more than 2 kinds.
As the above-mentioned functional group that comprises the hydrogen atom that can form hydrogen bond, for example can enumerate: carboxyl (pKa=4), phosphate (pKa=7) or phenolic group (pKa=10) etc.
The pKa of the above-mentioned functional group that comprises the hydrogen atom that can form hydrogen bond preferably in 2～10 scopes, more preferably in 3～9 scopes.Therefore if pKa is lower than 2, then the acidity of dispersion agent (F) is too high, is easy to promote the reaction as the epoxy composition and the trimethylene oxide composition of resinous principle.In addition, the package stability that also may cause its uncured state insulating trip reduces.If pKa surpasses 10, then possibly can't give full play to its function, and then cause fully to improve the thermal conductivity and the puncture of insulation characteristic of the cured article of insulating trip as dispersion agent (F).
The above-mentioned functional group that comprises the hydrogen atom that can form hydrogen bond is preferably carboxyl or phosphate.At this moment, the thermal conductivity and the puncture of insulation characteristic of the cured article of insulating trip are further enhanced.
As dispersion agent (F), specifically for example can enumerate: polyester carboxylic acid, polyethers carboxylic acid, polyacrylic carboxylic acid, aliphatic carboxylic acid, polysiloxane-based carboxylic acid, polyester phosphoric acid, polyethers phosphoric acid, polyacrylic phosphoric acid, aliphatics phosphoric acid, polysiloxane-based phosphoric acid, polyester phenol, polyethers phenol, polyacrylic phenol, aliphatics phenol or polysiloxane-based phenol etc.
When using the filler (D4) of process pulverizing, the tendency that serious cohesion takes place is arranged between contacted crushed face.Therefore, when the filler (D4) that uses process to pulverize, be difficult to make filler (D4) to be dispersed in the insulating trip with high-density through pulverizing.So, may cause the puncture of insulation characteristic and the thermal conductivity of cured article of operability, the insulating trip of its uncured state insulating trip to reduce., by when using, using above-mentioned dispersion agent (F), the filler (D4) through pulverizing is dispersed in the insulating trip with high-density through the filler of pulverizing (D4).So, the puncture of insulation characteristic and the thermal conductivity of cured article of operability, the insulating trip of its uncured state insulating trip is improved.
In insulating trip 100 weight %, the content of dispersion agent (F) preferably in 0.01～20 weight % scope, more preferably in 0.1～10 weight % scope.When the content of dispersion agent (F) is in this scope, can suppresses the cohesion of filler (D), and the thermal conductivity and the puncture of insulation characteristic of the cured article of insulating trip are further enhanced.
(rubber grain (E))
Can also contain rubber grain (E) in the insulating trip of the present invention.When containing rubber grain, can improve the stress relaxation of the cured article of insulating trip.
(E) there is no particular restriction for rubber grain.As rubber grain (E), for example can enumerate: acrylic rubber, divinyl rubber, synthetic polyisoprene, acrylonitrile-butadiene rubber, styrene butadiene rubbers, styrene isoprene rubber, urethanes, silicon rubber, viton or natural rubber etc.Proterties for rubber grain does not have particular restriction.
Rubber grain (E) is preferably silicone rubber particles.At this moment, can make the stress relaxation of insulating trip be able to further raising, and the flexibility of the cured article of insulating trip is further improved.
By rubber grain (E) and filler (D) are used in combination, can make insulating trip when showing low coefficient of linear thermal expansion, have the stress relaxation ability.So, though be exposed to this insulating trip under the high temperature or the cold cycling condition under, the cured article of insulating trip also is difficult for peeling off, cracking etc.
In insulating trip 100 weight %, the content of rubber grain (E) preferably in 0.1～40 weight % scope, more preferably in 0.3～20 weight % scope.If the content of rubber grain (E) is very few, then the cured article of insulating trip possibly can't show enough stress relaxation.If the content of rubber grain (E) is too much, then may cause the cementability of the cured article of insulating trip to reduce.
(other composition)
In order further to improve operability, can also contain body material materials such as woven fiber glass, glass non-woven fabrics or aramid nonwoven fabric in the insulating trip of the present invention.But, even do not contain above-mentioned body material material, insulating trip of the present invention also has shape-holding property and excellent operation under room temperature (23 ℃) under its uncured state.Therefore, preferably do not contain in the insulating trip body material material, especially preferably do not contain woven fiber glass.When not containing above-mentioned body material material in the insulating trip, can reduce the thickness of insulating trip, and can further improve the thermal conductivity of the cured article of insulating trip.In addition, optionally, can also easily carry out various processing such as laser processing, boring processing to insulating trip.Need to prove that described shape-holding property is meant: even under the situation that does not have supports such as PET film, Copper Foil, it also can keep sheet form under its uncured state, and with sheet-form it is handled.
In addition, as required, can also contain thixotropy imparting agent, dispersion agent, fire retardant or tinting material etc. in the insulating trip of the present invention.
As above-mentioned thixotropy imparting agent, polymeric amide (Port リ ア マ イ De) resin, fatty amide (lipid acid ア マ イ De) resin, polymeric amide (Port リ ア ミ De) resin or dioctyl phthalate (DOP) resin etc.
As above-mentioned dispersion agent, can enumerate anionic property dispersion agent, cationic dispersion agent or nonionic dispersion agent etc.
As above-mentioned anionic property dispersion agent, can enumerate fatty acid soaps, alkyl sodium sulfate ester, dialkyl sodium sulfosuccinate or sodium alkyl benzene sulfonate etc.As above-mentioned cationic dispersion agent, can enumerate decyl amine acetate, trimethyl ammonium chloride or dimethyl (benzyl) ammonium chloride etc.As above-mentioned nonionic dispersion agent, can enumerate polyglycol ether, macrogol ester, sorbitan ester, sorbitan ester ether, direactive glyceride, Polyglycerine alkyl ester, fatty diglycollic amide, alkyl, polyether amine, amine oxide or Unister E 275 etc.
As above-mentioned fire retardant, can enumerate metal hydroxides, Phosphorus compound, nitrogen compound, layered double-hydroxide ( Zhuan Complex water and thing), antimony compounds, bromine compounds or brominated Resins, epoxy etc.
As above-mentioned metal hydroxides, can enumerate aluminium hydroxide, magnesium hydroxide, dawsonite (dawsonite), aluminic acid calcium, two hydrated gypsum or calcium hydroxide etc.As above-mentioned Phosphorus compound, can enumerate phosphoric acid ester such as red phosphorus, ammonium polyphosphate, triphenylphosphate, tricyclohexyl phosphate or phosphorus or phosphorous resins such as phosphorous epoxy resin, phosphorous phenoxy resin or phosphorous vinyl compound etc.As above-mentioned nitrogen compound, can enumerate melamine compounds such as trimeric cyanamide, melamine cyanurate, trimeric cyanamide chlorinated isocyanurates or melamine phosphate and these melamine compounds are applied surface treatment and melamine derivative of obtaining etc.As above-mentioned layered double-hydroxide, can enumerate hydrotalcite etc.As above-mentioned antimony compounds, can enumerate ANTIMONY TRIOXIDE SB 203 99.8 PCT or antimony pentaoxide etc.As above-mentioned bromine compounds, can enumerate decabrominated dipheny base ether or triallyl isocyanurate hexabromide etc.As above-mentioned brominated Resins, epoxy, can enumerate tetrabromo-bisphenol etc.Wherein, preferably use metal hydroxides, Phosphorus compound, bromine compounds or melamine derivative.
As above-mentioned tinting material, can use pigment or dyestuffs such as carbon black, graphite, soccerballene, titanium carbide (チ タ Application カ one ボ Application), Manganse Dioxide or phthalocyanine.
(insulating trip)
The manufacture method of insulating trip of the present invention there is no particular restriction.For example, insulating trip can obtain by following method: utilize methods such as solvent cast method or film extrusion will mix mixture that above-mentioned materials obtains and be configured as sheet and obtain insulating trip.When being configured as sheet, preferably carry out deaeration.
The glass transition temperature Tg of its uncured state insulating trip is below 25 ℃.If second-order transition temperature surpasses 25 ℃, then insulating trip at room temperature may become hard and crisp.And then may cause the operability of its uncured state insulating trip to reduce.
The insulating trip of its uncured state the bending elastic modulus under 25 ℃ preferably in 10～1000MPa scope, more preferably in 20～500MPa scope.If the bending elastic modulus of its uncured state insulating trip under 25 ℃ is lower than 10MPa, then may cause its uncured state insulating trip shape-holding property at room temperature significantly to reduce, the operability of its uncured state insulating trip reduces.If the bending elastic modulus of its uncured state insulating trip under 25 ℃ surpasses 1000MPa, then its Young's modulus can't fully reduce when heat bonding, the cured article that may cause insulating trip fully driving fit and may cause that the cured article of insulating trip and the cementability between the adhering object thing reduce on the adhering object thing.
After insulating trip solidifies, the cured article of insulating trip the bending elastic modulus under 25 ℃ preferably in 1000～50000MPa scope, more preferably in 5000～30000MPa scope.If the bending elastic modulus of the cured article of insulating trip under 25 ℃ is lower than 1000MPa, then when for example using insulating trip to make the laminated substrate of thinner thickness or layered products such as veneer sheet that the two sides is provided with copper circuit, deflection takes place in the layered product of gained easily.Thus, layered product easily because of fracture, breakage such as bending.If the bending elastic modulus of the cured article of insulating trip under 25 ℃ surpasses 50000Mpa, then may cause the cured article of insulating trip to become excessively hard and crisp, cracking etc. takes place in the cured article that easily causes insulating trip.
Above-mentioned bending elastic modulus can be measured by following manner: for example, use universal testing machine RTC-1310A (manufacturing of ORIENTEC company), according to JIS K 7111 standards, under each condition of length of support 6cm and speed 1.5mm/ minute, the test film of long 8cm, wide 1cm and thick 4mm is measured.In addition, when the bending elastic modulus of the cured article of measuring insulating trip, the cured article of insulating trip can obtain under the 2 such phase temperature conditions by solidifying 1 hour and then solidified under 200 ℃ at 120 ℃ in 1 hour.
For insulating trip of the present invention, when adopting rotary-type Measurement of Dynamic Viscoelasticity device to measure, preferred its uncured state insulating trip at the tan δ under 25 ℃ in 0.1～1.0 scope, and when 25 ℃ were warming up to 250 ℃, the maximum value of the tan δ of insulating trip was preferably in 1.0～5.0 scopes at the insulating trip that makes its uncured state.The tan8 of above-mentioned insulating trip is more preferably in 0.1～0.5 scope.The maximum value of the tan δ of above-mentioned insulating trip is more preferably in 1.5～4.0 scopes.
If the tan δ of above-mentioned its uncured state insulating trip under 25 ℃ is lower than 0.1, then can cause the flexibility of its uncured state insulating trip to reduce, its uncured state insulating trip is damaged easily.If the tan δ of above-mentioned its uncured state insulating trip under 25 ℃ more than 1.0, then because its uncured state insulating trip can become too soft, therefore may cause the operability of its uncured state insulating trip to reduce.
At the insulating trip that makes above-mentioned its uncured state when 25 ℃ are warming up to 250 ℃, if the maximum value of the tan δ of insulating trip is lower than 1.0, then may cause when heat bonding insulating trip fully driving fit on the adhering object thing.If the maximum value of the tan δ of above-mentioned insulating trip surpasses 5.0, then the flowability of insulating trip can become too high, and the thickness attenuation of insulating trip in the time of may causing heat bonding can't obtain ideal puncture of insulation characteristic.
The tan δ of above-mentioned its uncured state insulating trip under 25 ℃ can measure by following manner: adopt rotary-type Measurement of Dynamic Viscoelasticity device VAR-100 (manufacturing of REOLOGICA Instruments company), utilize the discoideus its uncured state insulating trip of diameter 2cm, by parallel (parallel) type flat board of diameter 2cm, measuring under the condition with oscillatory deformation master mode, initial stress 10Pa, frequency 1Hz and strain 1% under 25 ℃.In addition, the tan δ maximum value of its uncured state insulating trip insulating trip when 25 ℃ are warming up to 250 ℃ can be measured by following method: except the said determination condition, the insulating trip that makes above-mentioned its uncured state is warming up to 250 ℃ with 30 ℃/minute heat-up rate from 25 ℃ and measures.
When above-mentioned bending elastic modulus and tan δ were in above-mentioned specified range, the operability that its uncured state insulating trip reaches when using during fabrication can obviously improve.And when using insulating trip to be bonded in high heat conductive bodies such as Copper Foil, aluminium sheet on the conductive layer, bonding strength can significantly increase.In addition, when existing on the bonding plane of above-mentioned high heat conductive body when concavo-convex, can improve insulating trip for this concavo-convex servo-actuated.So, be difficult for forming the space at bonding interface, and then can improve thermal conductivity.
Need to prove, when the filler of filling high thermal conductivity coefficient with high-density in the insulation adhesive sheet of record in patent documentation 4 improves exothermicity, can cause that the Young's modulus of insulation adhesive sheet increases, thereby no longer satisfy the parameter of record in the patent documentation 4.In addition, if when the filler of filling high thermal conductivity coefficient with high-density improves the exothermicity thermal conductivity, make it satisfy the parameter of record in the patent documentation 4, must add a large amount of low molecular weight compositions and come viscosity is adjusted.And can cause the tackiness of the insulation adhesive sheet of its uncured state to become too high this moment, may cause that operability reduces.
In addition, under solid state, stress relaxation occurs, in the insulation adhesive sheet of patent documentation 4 records, cooperate Tg at the acrylic rubber more than-10 ℃ in order to make insulating trip., when adding this rubber constituent, cause that easily the thermotolerance of the cured article of insulation adhesive sheet reduces.So, the insulation adhesive sheet of patent documentation 4 record may be used for the electronic unit heat release be the purposes of purpose, especially because of apply high-voltage or greatly electric current produce the purposes of the power-equipments such as electromobile of high calorie.
When above-mentioned bending elastic modulus and tan δ are in above-mentioned specified range, the operability of its uncured state insulating trip is improved.And, insulating trip can be used for the power-equipment purposes.
The reactivity of its uncured state insulating trip is preferably below 10%.If the reactivity of its uncured state insulating trip surpasses 10%, then its uncured state insulating trip can become hard and crisp, and then may cause that its uncured state insulating trip operability at room temperature reduces, the cementability of the cured article of insulating trip reduces.The reactivity of insulating trip can be obtained by following method: adopt differential scanning type calorimetric measurement device make insulating trip 120 ℃ solidify 1 hour, solidified 1 hour the heat Calculation that in 2 such stage solidification, produces by insulating trip and obtain the reactivity of insulating trip down at 200 ℃.
Thickness for insulating trip there is no particular restriction.The thickness of insulating trip preferably in 10～300 mu m ranges, more preferably in 50～200 mu m ranges, further preferably in 70～120 mu m ranges.If thickness is thin excessively, then may cause the reduction of puncture of insulation characteristic, the insulativity of the cured article of insulating trip to descend.If thickness is blocked up, may cause when being bonded in metallic object on the conductive layer that then exothermicity descends.
By increasing the thickness of insulating trip, the puncture of insulation characteristic of the cured article of insulating trip is further improved.Even but the thickness of insulating trip of the present invention is thinner, the cured article of insulating trip also can have high puncture of insulation characteristic.
The thermal conductivity of the cured article of insulating trip preferably more than the 1.5W/mK, more preferably more than the 2.0W/mK, further preferably more than the 3.0W/mK, be more preferably at more than the 5.0W/mK, especially preferably more than 7.0W/mK.If thermal conductivity is low excessively, then may cause the exothermicity deficiency of the cured article of insulating trip.
After insulating trip solidified, the breakdown voltage of the cured article of insulating trip was more than 30kV/mm.The breakdown voltage of the cured article of insulating trip is preferably more than the 40kV/mm, more preferably more than the 50kV/mm, further preferably more than the 80kV/mm, especially preferably more than 100kV/mm.
In the composition as the insulating resin composition of insulating trip of the present invention, contain following each composition with above-mentioned specified quantitative: polymkeric substance (A), its weight-average molecular weight is the aromatic series skeleton at its skeleton with proof voltage excellence more than 10,000; At least a monomer (B) in epoxy monomer (B1) and the oxetane monomer (B2), the weight-average molecular weight of described epoxy monomer (B1) is below 600 and have an aromatic series skeleton, and the weight-average molecular weight of described oxetane monomer (B2) is below 600 and have an aromatic series skeleton; Solidifying agent (C), this solidifying agent has excellent proof voltage, is resol or has the aromatic series skeleton or the acid anhydrides of ester ring type skeleton, the hydrogenation thing of this acid anhydrides or the modifier of this acid anhydrides.Thus, can make the breakdown voltage of insulating resin composition itself be higher than 30kV/mm.In addition, for disperseing Packed insulating trip in the insulating resin composition, insulating resin composition in its cured article and filler the common practise that puncture of insulation is this area easily takes place at the interface.Therefore, when having the insulating resin composition when the dispersion state of filler really between good and filler, because the interface of insulating resin composition and filler can become discontinuous in insulating trip inside, thereby its breakdown voltage can remain in the high value.And when the dispersion state of filler when there is thick filler aggregate in insufficient and insulating trip inside, because the interface of insulating resin composition and filler is continuous, thereby its breakdown voltage can significantly reduce.That is, the breakdown voltage of the cured article of insulating trip is lower than 30kV/mm and then means: the dispersion state of filler in the insulating resin composition is insufficient.If the breakdown voltage of the cured article of insulating trip is lower than 30kV/mm, then the dispersion state of filler in the insulating resin composition is insufficient, thereby may cause the cementability of the cured article of insulating trip to reduce.In addition, because local inequality easily takes place the sheet strength of insulating trip, thereby may cause that the operability of its uncured state insulating trip reduces.In addition, if breakdown voltage is low excessively, then when insulating trip being applied to the big current applications that electronic component for example uses, possibly can't obtain enough insulativity.
The volume specific resistance of the cured article of insulating trip is preferably 10 14More than the Ω cm, more preferably 10 16More than the Ω cm.If volume specific resistance is low excessively, then possibly can't keep the insulation between conductor layer and high heat conductive body.
The thermal linear expansion coefficient of the cured article of insulating trip is preferably below 30ppm/ ℃, more preferably below 20ppm/ ℃.If thermal linear expansion coefficient is too high, then may cause the cold-resistant thermal cycling reduction of the cured article of insulating trip.
(laminate structures)
Insulating trip of the present invention is used for the heat conductor of thermal conductivity more than 10W/mK is bonded in conductive layer.In addition, insulating trip of the present invention is suitable for use in the insulation layer that constitutes laminate structures, and described laminate structures presses conductive layer to form by being situated between by the upper strata of one side at least of the heat conductor of insulation layer more than thermal conductivity 10W/mK.
Layered product of the present invention comprises: thermal conductivity the heat conductor more than the 10W/mK, be laminated to the insulation layer on the one side at least of heat conductor and be laminated to insulation layer with lamination the opposite conductive layer on simultaneously of the face of heat conductor is arranged.This insulation layer is solidified to form by making the insulating trip with formation of the present invention.
Above-mentioned laminate structures can obtain by following method: for example, be provided with on the two sides on the veneer sheet of copper circuit or each conductive layer such as multiwiring board, Copper Foil, copper coin, semiconductor element or semiconductor subassembly after the bonded metal body by insulating trip being situated between, insulating trip is solidified and obtain described laminate structures.
Fig. 1 schematically shows the laminate structures in the one embodiment of the present invention for part intercepts front cross-sectional view.
Laminate structures 1 as shown in Figure 1, on the surperficial 2a as the conductive layer 2 of heat releasing source, being situated between has heat conductor 4 by insulation layer 3 laminations.Insulation layer 3 is solidified to form by making insulating trip of the present invention.As heat conductor 4, can use the heat conductor of thermal conductivity more than 10W/mK.
In laminate structures 1, because insulation layer 3 has high thermal conductivity coefficient, the heat that therefore comes from conductive layer 2 sides is easy to conduct to above-mentioned heat conductor 4 by insulation layer 3.In laminate structures 1, can realize efficiently radiates heat by this heat conductor 4.
There is not particular restriction for the heat conductor of above-mentioned thermal conductivity more than 10W/mK.As the heat conductor of above-mentioned thermal conductivity more than 10W/mK, for example can enumerate: aluminium, copper, aluminum oxide, beryllium oxide, silicon carbide, silicon nitride, aluminium nitride or graphite flake etc.Wherein, the heat conductor of described thermal conductivity more than 10W/mK is preferably copper or aluminium.Copper or aluminium have excellent exothermicity.
Insulating trip of the present invention is applicable to thermal conductivity is bonded at the heat conductor more than the 10W/mK on the conductive layer of semiconductor device that described semiconductor device is the semiconductor device that semiconductor element is installed on the substrate.Insulating trip of the present invention is applicable to thermal conductivity is bonded at the heat conductor more than the 10W/mK on the conductive layer of electronic part apparatus that described electronic part apparatus is the electronic part apparatus that is equipped with other electronic unit element except semiconductor element on the substrate.
When semiconductor element is a big electric current during with the electric power equipment component,, can seek higher insulativity or thermotolerance etc. for the cured article of insulating trip.Therefore, be suitable for insulating trip of the present invention is used for this class purposes.
Below, enumerate specific embodiments of the invention and comparative example illustrates the present invention.But the present invention is not limited to following embodiment.
Prepared following material.
[polymkeric substance (A)]
(1) contains the styrene resin (Nof Corp. makes, trade(brand)name: MarproofG-1010S, Mw=100,000, Tg=93 ℃, aromatic series skeleton shared ratio in whole skeleton 100 weight % is 65 weight %) of epoxide group
(2) bisphenol A-type phenoxy resin (japan epoxy resin company makes, trade(brand)name: E1256, Mw=51,000, Tg=98 ℃, aromatic series skeleton shared ratio in whole skeleton 100 weight % is 51 weight %)
(3) high heat-resisting phenoxy resin (Dongdu company that changes into makes, trade(brand)name: FX-293, Mw=43,700, Tg=163 ℃, aromatic series skeleton shared ratio in whole skeleton 100 weight % is 70 weight %)
[other polymkeric substance except that polymkeric substance (A)]
(1) contains the acrylic resin 1 (Nof Corp. make, trade(brand)name: MarproofG-0130S, Mw=9,000, Tg=69 ℃) of epoxide group
(2) acrylonitrile butadiene rubber (Nippon Zeon Co., Ltd. makes, trade(brand)name: Nipol 1001, Mw=30,000, aromatic series skeleton shared ratio in whole skeleton 100 weight % is 0%)
(3) contain the acrylic resin 2 (Nof Corp. makes, trade(brand)name: MarproofG-01100, Mw=12,000, Tg=47 ℃, aromatic series skeleton shared ratio in whole skeleton 100 weight % is 0%) of epoxide group
[epoxy monomer (B1)]
(1) the bisphenol A-type liquid-state epoxy resin (the japan epoxy resin manufacturing, trade(brand)name: Epicot 828US, Mw=370)
(2) Bisphenol F type liquid-state epoxy resin (the japan epoxy resin manufacturing, trade(brand)name: Epicot 806L, Mw=370)
(3) trifunctional glycidyl diamines type liquid-state epoxy resin (japan epoxy resin company makes, trade(brand)name: Epicot 630, Mw=300)
(4) fluorene skeleton Resins, epoxy (gas chemical company in Osaka makes, trade(brand)name: Oncoat EX1011, Mw=486)
(5) naphthalene skeleton liquid-state epoxy resin (big Japanese ink chemical company makes, trade(brand)name: EPICLONHP-4032D, Mw=304)
[oxetane monomer (B2)]
(1) benzene skeleton oxetane resin (emerging product company of space portion makes, trade(brand)name: ETERNACOLLOXTP, Mw=362.4)
[demonomerization (B) other monomer in addition]
(1) hexahydrophthalic acid skeleton liquid-state epoxy resin (Japanese chemical drug corporate system is made trade(brand)name: AK-601, Mw=284)
(2) the bisphenol A-type solid epoxy resin (japan epoxy resin company makes, trade(brand)name: 1003, Mw=1300)
[solidifying agent (C)]
(1) (new Japanese physics and chemistry company makes trade(brand)name: MH-700) to ester ring type skeleton acid anhydrides
(2) (Sartomer Japan company makes aromatic series skeleton acid anhydrides, trade(brand)name: SMA RESINEF60)
(3) (new Japanese physics and chemistry company makes trade(brand)name: HNA-100) to greasiness ring type skeleton acid anhydrides
(4) (japan epoxy resin company makes terpenes skeleton acid anhydrides, trade(brand)name: EPICURE YH-306)
(5) (the bright and company that changes into makes trade(brand)name: MEH-7851-S) to biphenyl backbone resol
(6) (japan epoxy resin company makes allyl group skeleton resol, trade(brand)name: YLH-903)
(7) (big Japanese ink chemical company makes trade(brand)name: PhenolightKA-7052-L2) to triazine skeleton resol
(8) (the flourish chemical industrial company of group makes trade(brand)name: PS-6492) to trimeric cyanamide skeleton resol
(9) (the imidazoles curing catalyst, four countries change into company and make the solid dispersing imidazoles of tricarbimide modification, trade(brand)name: 2MZA-PW)
[filler (D)]
(1) surface-hydrophobicized aerosil (Tokuyama company makes, trade(brand)name: MT-10, median size 15nm, thermal conductivity 1.3W/mK)
(2) spherical alumina 1 (Denka company makes, trade(brand)name: DAM-10, median size 10 μ m, thermal conductivity 36W/mK)
(3) boron nitride (clear and electrician company makes trade(brand)name: UHP-1, median size 8 μ m, thermal conductivity 60W/mK)
(4) aluminium nitride (Toyo Aluminium company makes, trade(brand)name: TOYALNITE-FLX, median size 14 μ m, thermal conductivity 200W/mK)
(5) silicon carbide (Shinano Electric Refining company makes, trade(brand)name: Shinano-Rundum GP#700, median size 17 μ m)
(6) spherical alumina 2 (ball filler (D1), sumitomo chemical company manufacturing, trade(brand)name: AKP-30, median size 0.4 μ m, length-to-diameter ratio 1.1～2.0, thermal conductivity 36W/mK)
(7) spherical magnesium oxide (ball filler (D1), Sakai chemical industrial company makes, trade(brand)name: SMOSmall Particle, median size 0.1 μ m, length-to-diameter ratio 1.1～1.5, thermal conductivity 42W/mK)
(8) spherical alumina 3 (ball filler (D2), Denka company makes, trade(brand)name: DAM-05, median size 5 μ m, length-to-diameter ratio 1～1.2, thermal conductivity 36W/mK)
(9) spherical aluminium nitride 1 (ball filler (D2), Toyo Aluminium company makes, trade(brand)name: TOYALNITE-FLC, median size 3.7 μ m, length-to-diameter ratio 1～1.3, thermal conductivity 200W/mK)
(10) spherical alumina 4 (ball filler (D3), ADMATECHS company makes, trade(brand)name: AO-820, median size 20 μ m, length-to-diameter ratio 1～1.1, thermal conductivity 36W/mK)
(11) spherical aluminium nitride 2 (ball filler (D3), Toyo Aluminium company makes, trade(brand)name: TOYALNITE-FLD, median size 30 μ m, length-to-diameter ratio 1～1.3, thermal conductivity 200W/mK)
(12) spherical alumina 5 (sumitomo chemical company manufacturing, trade(brand)name: AA-07, median size 0.7 μ m, length-to-diameter ratio 1.1～2.0, thermal conductivity 36W/mK)
(13) 5 μ m aluminum oxide (pulverize filler (D4), Japanese light metal company makes, trade(brand)name: LT300C, median size 5 μ m)
(14) 2 μ m aluminum oxide (pulverize filler (D4), Japanese light metal company makes, trade(brand)name: LS-242C, median size 2 μ m)
(15) 1.2 μ m aluminium nitride (pulverize filler (D4), Japan aluminium company makes, trade(brand)name: JC, median size 1.2 μ m)
(16) 29 μ m aluminum oxide (pulverize filler (D4), Pacific Rundum company makes, trade(brand)name: LA400, median size 29 μ m)
[dispersion agent (F)]
(1) acrylic dispersants (BYK-Chemie Japan company makes, and trade(brand)name: Disperbyk-2070 has pKa and be 4 carboxyl)
(2) polyethers dispersion agent (the nanmu company that originally changes into makes, and trade(brand)name: ED151 has pKa and be 7 phosphate)
[other dispersion agent except that dispersion agent (F)]
(1) nonionic class dispersion agent (this dispersion agent does not have the functional group that comprises the hydrogen atom that can form hydrogen bond for the manufacturing of chemical company of common prosperity society, trade(brand)name: D-90)
[rubber grain (E)]
(1) nucleocapsid type rubber particulate (MITSUBISHI RAYON company makes, and trade(brand)name: KW4426 has the shell that formed by methyl methacrylate and the rubber particle of the nuclear that formed by butyl acrylate, median size 5 μ m)
(2) silicon rubber particulate (Toray Dow Corning company makes, trade(brand)name: Trefil E601, median size 2 μ m)
[additive]
(1) (chemical company of SHIN-ETSU HANTOTAI makes epoxy silane coupling, trade(brand)name: KBE403)
[solvent]
(1) methyl ethyl ketone
(embodiment 1)
Adopt HomoDisper type stirrer,, and carry out mixingly, prepared insulating material according to each compound of mixed shown in the following table 1.
The insulating material of gained is coated on the demoulding PET sheet material of thickness 50 μ m, makes the thickness of this material reach 100 μ m,, thereby on the PET sheet material, made insulating trip again 90 ℃ baking oven inner drying 30 minutes.
(embodiment 2～18, reference example 1 and comparative example 1～3)
Except the kind of the compound that will use and use level according to changing shown in following table 1～3, made insulating material according to the method identical, thereby on the PET sheet material, made insulating trip with embodiment 1.
(to the evaluation of the insulating trip of embodiment 2～18, reference example 1 and comparative example 1～3)
(1) operability
Cut the laminate that has the PET sheet material and be formed on the insulating trip on this PET sheet material, make this laminate that cuts have the planeform of 460mm * 610mm, thereby obtained specimen.The specimen that use obtains is being estimated the operability when the PET sheet material is peeled off its uncured state insulating trip according to following standard under the room temperature (23 ℃).
[judgement criteria of operability]
Zero: insulating trip does not deform, and can easily peel off insulating trip
△: the peelable insulation sheet, but sheet material elongation or fracture take place
*: can't peel off insulating trip
(2) second-order transition temperature
The differential scanning calorimetric measurement device " DSC220C " that adopts Seiko Instruments company to make is measured the second-order transition temperature of its uncured state insulating trip with 3 ℃/minute heat-up rates.
(3) thermal conductivity
The thermal conductivity meter " quick conductive coefficient measuring instrument QTM-500 " that adopts capital of a country Electronics Industry Company to make is measured the thermal conductivity of insulating trip.
(4) stripping strength
Insulating trip is clipped between the thick electrolytic copper foil of the thick aluminium sheet of 1mm and 35 μ m, when keeping 4MPa pressure,,, thereby has formed copper clad laminate the insulating trip cure under pressure 120 ℃ of compactings 1 hour down, again 200 ℃ of compactings 1 hour down with vacuum press.Copper Foil to the gained copper clad laminate carries out etching, thereby has formed the band of the Copper Foil of wide 10mm.Then, Copper Foil is peeled off, measured the stripping strength of this moment with draw speed with respect to the angle of 90 ° of substrates, 50mm/ minute.
(5) breakdown voltage
Cut insulating trip, make its planeform, thereby obtained specimen with 100mm * 100mm.Make the specimen that obtains in 120 ℃ baking oven, solidify 1 hour, in 200 ℃ baking oven, solidified 1 hour again, thereby obtained the cured article of insulating trip.Adopt electrical-resistance test device (MODEL7473, EXTECH electronics, inc. make), between the cured article of insulating trip, apply voltage of alternating current, make voltage with the 1kV/ speed rising in second.Voltage with insulating trip when breakdown is as breakdown voltage.
(6) scolding tin oven test
Insulating trip is clipped between the thick electrolytic copper foil of the thick aluminium sheet of 1mm and 35 μ m, when keeping 4MPa pressure,, 200 ℃ of compactings 1 hour down,, thereby has formed copper clad laminate again the insulating trip cure under pressure 120 ℃ of compactings 1 hour down with vacuum press.Gained is covered the size that the copper laminated substrate is cut into 50mm * 60mm, thereby obtained specimen.The specimen Copper Foil side that obtains is floated in 288 ℃ the solder bath down, measure the time till Copper Foil is heaved or peeled off, and judge according to following standard.
[criterion of scolding tin oven test]
Zero: do not heave yet or peeled off through 3 minutes
△: after through 1 minute, before arriving 3 minutes, heave or peel off
*: heave before through 1 minute or peel off
(7) reactivity
The differential scanning type calorimetric measurement device " DSC220C " that adopts Seiko Instruments company to make, make the insulating trip that obtains with the heat-up rate of 30 ℃ mensuration starting temperature and 8 ℃/minute be warming up to 120 ℃ and keep 1 hour after, further be warming up to 200 ℃ and kept 1 hour with 8 ℃/minute heat-up rate again.The heat (following note is made heat A) that produces when insulating trip is solidified is measured.
Then, except the insulating material that will prepare in the insulating trip production process of embodiment and comparative example is coated on the demoulding PET sheet material that thickness is 50 μ m, makes its thickness reach 100 μ m, and make it beyond under the normal temperature and vacuum conditions of 23 ℃ and 0.01 air pressure dry 1 hour, prepared the insulating trip of its uncured state that obtains with non-type of heating drying according to the method identical with embodiment and comparative example.The heat (following note is made heat B) that it is produced during with two stage solidification according to method identical when measuring above-mentioned heat A is measured.Utilize following formula, obtained the reactivity of its uncured state insulating trip by heat A that obtains and heat B.
Reactivity (%)=[1-(heat A/ heat B)] * 100
The result is shown in following table 1～3.
[table 1]
Figure GPA00001045404100341
The content ratio of ※ 1 in all resins composition 100 weight % of insulating trip
The content ratio of ※ 2 in insulating trip 100 volume %
[table 2]
Figure GPA00001045404100351
The content ratio of ※ 1 in all resins composition 100 weight % of insulating trip
The content ratio of ※ 2 in insulating trip 100 volume %
[table 3]
Figure GPA00001045404100361
The content ratio of ※ 1 in all resins composition 100 weight % of insulating trip
The content ratio of ※ 2 in insulating trip 100 volume %
(embodiment 19～44 and comparative example 4～8)
Except the kind of the compound that will use and use level according to changing shown in following table 4～7, prepared insulating material according to the method identical, thereby on the PET sheet material, made insulating trip with embodiment 1.
(to the evaluation of the insulating trip of embodiment 19～44 and comparative example 4～8)
Adopt the assessment item of above-mentioned (1) operability, (2) second-order transition temperature, (4) stripping strength, (5) breakdown voltage and (7) reactivity that insulating trip is estimated.And insulating trip is estimated at the assessment item of the distribution of following (3-2) thermal conductivity, (6-2) scolding tin oven test and (8) filler.
(3-2) thermal conductivity
Insulating trip was heated 1 hour under 120 ℃ in baking oven and then heated 1 hour down, it is solidified, thereby obtained the cured article of insulating trip at 200 ℃.Adopt thermal conductivity meter " quick conductive coefficient measuring instrument QTM-500 " that capital of a country Electronics Industry Company makes that the thermal conductivity of the cured article of the insulating trip that obtains is measured.
(6-2) scolding tin oven test
Except the criterion of scolding tin oven test being carried out change as described below, estimate according to the mode identical with (6) scolding tin oven test.
[criterion of scolding tin oven test]
◎: do not heave yet or peeled off through 10 minutes
Zero: after through 3 minutes, before arriving 10 minutes, heave or peel off
△: after through 1 minute, before arriving 3 minutes, heave or peel off
*: heave before through 1 minute or peel off
(8) size-grade distribution of filler
Utilize laser diffraction formula particle size distribution device that the size-grade distribution of whole fillers (D) of comprising in the insulating trip is measured.Based on measurement result, begun to calculate the cumulative volume of filler (D) from small particle size filler, obtained the cumulative volume % at particle diameter 0.1 μ m, 0.5 μ m, 2.0 μ m, 6.0 μ m and 10.0 μ m places thus.
The result is shown in following table 4～7.
[table 4]
Figure GPA00001045404100381
The content ratio of ※ 1 in all resins composition 100 weight % of insulating trip
The content ratio of ※ 2 in filler (D) 100 volume %
The content ratio of ※ 3 in insulating trip 100 volume %
[table 5]
Figure GPA00001045404100391
The content ratio of ※ 1 in all resins composition 100 weight % of insulating trip
The content ratio of ※ 2 in filler (D) 100 volume %
The content ratio of ※ 3 in insulating trip 100 volume %
[table 6]
Figure GPA00001045404100401
The content ratio of ※ 1 in all resins composition 100 weight % of insulating trip
The content ratio of ※ 2 in filler (D) 100 volume %
The content ratio of ※ 3 in insulating trip 100 volume %
[table 7]
Figure GPA00001045404100411
The content ratio of ※ 1 in all resins composition 100 weight % of insulating trip
The content ratio of ※ 2 in filler (D) 100 volume %
The content ratio of ※ 3 in insulating trip 100 volume %
(embodiment 45～62 and comparative example 9～13)
Except the kind of the compound that will use and use level according to changing shown in following table 8～10, prepared insulating material according to the method identical, and on the PET sheet material, made insulating trip with embodiment 1.
(to the evaluation of the insulating trip of embodiment 45～62 and comparative example 9～13)
Adopt the assessment item of above-mentioned (1) operability, (2) second-order transition temperature, (3) thermal conductivity, (4) stripping strength, (5) breakdown voltage, (6) scolding tin oven test and (7) reactivity that insulating trip is estimated.And insulating trip is estimated at the assessment item of following (9) shape-holding property.
(9) shape-holding property
In the evaluation of above-mentioned (1) operability, prepared the insulating trip of its uncured state after the PET sheet material is peeled off.Fix four angles of the insulating trip of this its uncured state, insulating trip is unsettled, and these four angles are positioned on the direction that is parallel to horizontal direction, under 23 ℃, placed 10 minutes.Distortion to the insulating trip after placing is observed, and according to following standard determination shape-holding property.
[criterion of shape-holding property]
Zero: insulating trip is crooked downwards, and the deflection distance of insulating trip in the vertical direction (deformation extent) is in 5cm
△: insulating trip is crooked downwards, and the deflection distance of insulating trip in the vertical direction (deformation extent) surpasses 5cm
*: insulating trip breaks
The result is shown in following table 8～10.
[table 8]
Figure GPA00001045404100431
The content ratio of ※ 1 in all resins composition 100 weight % of insulating trip
The content ratio of ※ 2 in insulating trip 100 volume %
The content ratio of ※ 3 in insulating trip 100 weight %
[table 9]
Figure GPA00001045404100441
The content ratio of ※ 1 in all resins composition 100 weight % of insulating trip
The content ratio of ※ 2 in insulating trip 100 volume %
The content ratio of ※ 3 in insulating trip 100 weight %
[table 10]
Figure GPA00001045404100451
The content ratio of ※ 1 in all resins composition 100 weight % of insulating trip
The content ratio of ※ 2 in insulating trip 100 volume %
The content ratio of ※ 3 in insulating trip 100 weight %
(embodiment 63～81 and comparative example 14～16)
Except the kind of the compound that will use and use level according to changing shown in following table 11～13, prepared insulating material according to the method identical, thereby on the PET sheet material, made insulating trip with embodiment 1.
(to the evaluation of the insulating trip of embodiment 63～81 and comparative example 14～16)
Assessment item at above-mentioned (1) operability, (9) shape-holding property, (2) second-order transition temperature, (3) thermal conductivity, (4) stripping strength, (5) breakdown voltage, (6) scolding tin oven test and (7) reactivity is estimated insulating trip.
The result is shown in following table 11～13.
[table 11]
Figure GPA00001045404100461
The content ratio of ※ 1 in all resins composition 100 weight % of insulating trip
The content ratio of ※ 2 in insulating trip 100 volume %
[table 12]
Figure GPA00001045404100471
The content ratio of ※ 1 in all resins composition 100 weight % of insulating trip
The content ratio of ※ 2 in insulating trip 100 volume %
[table 13]
Figure GPA00001045404100481
The content ratio of ※ 1 in all resins composition 100 weight % of insulating trip
The content ratio of ※ 2 in insulating trip 100 volume %
(embodiment 82～101 and comparative example 17～20)
Except the kind of the compound that will use and use level according to changing shown in following table 14～17, prepared insulating material according to the method identical, and on the PET sheet material, made insulating trip with embodiment 1.
(to the evaluation of the insulating trip of embodiment 82～101 and comparative example 17～20)
Assessment item at above-mentioned (2) second-order transition temperature, (3) thermal conductivity, (4) stripping strength, (5) breakdown voltage, (6) scolding tin oven test and (7) reactivity is estimated insulating trip.And insulating trip is estimated at the assessment item of following (1-2) operability, (9-2) shape-holding property, (10) exothermicity, (11) bending elastic modulus and (12) Young's modulus.
(1-2) operability
Except the criterion of operability being carried out change as described below, estimate according to the method identical with (1) operability.
[judgement criteria of operability]
◎: insulating trip does not deform, and can easily peel off; Do not show tackiness, be highly susceptible to operation
Zero: insulating trip does not deform, and can easily peel off; But, show small tackiness, must be noted during operation
△: the peelable insulation sheet, but sheet material elongation or fracture have taken place
*: can't peel off insulating trip
(9-2) shape-holding property
Except the criterion of shape-holding property being carried out change as described below, estimate according to the method identical with (9) shape-holding property.
[criterion of shape-holding property]
◎: insulating trip is crooked downwards, and the deflection distance of insulating trip in the vertical direction (deformation extent) is in 1cm
Zero: insulating trip is crooked downwards, and the deflection distance of insulating trip in the vertical direction (deformation extent) is above 1cm and in 3cm
△: insulating trip is crooked downwards, and the deflection distance of insulating trip in the vertical direction (deformation extent) is above 3cm and in 5cm
*: insulating trip is crooked downwards, and the deflection distance of insulating trip in the vertical direction (deformation extent) surpasses 5cm, or insulating trip takes place breaks
(10) exothermicity
Insulating trip is clipped between the thick electrolytic copper foil of the thick aluminium sheet of 1mm and 35 μ m, when keeping 4MPa pressure,,, thereby has formed copper clad laminate the insulating trip cure under pressure 120 ℃ of compactings 1 hour down, again 200 ℃ of compactings 1 hour down with vacuum press.With 20kgf/cm 2Pressure press on the copper-clad surface of gained copper clad laminate measure-alike and temperature control on the radiator body of 100 ℃ surface smoothing.With the temperature of thermocouple measurement surface of aluminum plate, and exothermicity is judged according to following standard.
[criterion of exothermicity]
◎: the temperature head of radiator body and surface of aluminum plate is in 3 ℃
Zero: the temperature head of radiator body and surface of aluminum plate is greater than 3 ℃ and in 6 ℃
△: the temperature head of radiator body and surface of aluminum plate is greater than 6 ℃ and in 10 ℃
*: the temperature head of radiator body and surface of aluminum plate is above 10 ℃
(11) bending elastic modulus
Adopt universal testing machine RTC-1310A (manufacturing of ORIENTEC company), according to JIS K 7111 standards, under each condition of length of support 6cm and speed 1.5mm/ minute, the test film of long 8cm, wide 1cm and thick 4mm is measured, measured the bending elastic modulus of its uncured state insulating trip under 25 ℃.
In addition, make insulating trip curing 1 hour under 120 ℃, solidified 1 hour down at 200 ℃ again, obtained the cured article of insulating trip.According to the method identical with its uncured state insulating trip, adopt universal testing machine (manufacturing of ORIENTEC company), according to JIS K 7111 standards, under the condition of length of support 6cm and speed 1.5mm/ minute, the test film of long 8cm, wide 1cm and thick 4mm is measured, measured the bending elastic modulus of cured article under 25 ℃ of gained insulating trip.
(12) Young's modulus
Adopt rotary-type Measurement of Dynamic Viscoelasticity device VAR-100 (manufacturing of REOLOGICA Instruments company), utilize the discoideus its uncured state insulating trip sample of diameter 2cm, by the parallel type flat board of diameter 2cm, measured the tan δ of its uncured state insulating trip under 25 ℃ under the condition with oscillatory deformation master mode, initial stress 10Pa, frequency 1Hz and strain 1%.In addition, the insulating trip that makes its uncured state tan δ maximum value of insulating trip when 25 ℃ are warming up to 250 ℃ is measured by following manner: except the said determination condition, the insulating trip sample that makes above-mentioned its uncured state is warming up to 250 ℃ with 30 ℃/minute heat-up rate from 25 ℃ and measures.
The result is shown in following table 14～17.
[table 14]
Figure GPA00001045404100511
The content ratio of ※ 1 in all resins composition 100 weight % of insulating trip
The content ratio of ※ 2 in insulating trip 100 volume %
※ 3 adopts rotary-type Measurement of Dynamic Viscoelasticity device to measure
[table 15]
Figure GPA00001045404100521
The content ratio of ※ 1 in all resins composition 100 weight % of insulating trip
The content ratio of ※ 2 in insulating trip 100 volume %
※ 3 adopts rotary-type Measurement of Dynamic Viscoelasticity device to measure
[table 16]
The content ratio of ※ 1 in all resins composition 100 weight % of insulating trip
The content ratio of ※ 2 in insulating trip 100 volume %
※ 3 adopts rotary-type Measurement of Dynamic Viscoelasticity device to measure
[table 17]
Figure GPA00001045404100541
The content ratio of ※ 1 in all resins composition 100 weight % of insulating trip
The content ratio of ※ 2 in insulating trip 100 volume %
※ 3 adopts rotary-type Measurement of Dynamic Viscoelasticity device to measure

Claims (19)

1. insulating trip, this insulating trip is used for the heat conductor of thermal conductivity more than 10W/mK is bonded in conductive layer, and wherein, this insulating trip contains:
Polymkeric substance (A), its weight-average molecular weight is more than 10,000 and have an aromatic series skeleton;
At least a monomer (B) in epoxy monomer (B1) and the oxetane monomer (B2), the weight-average molecular weight of described epoxy monomer (B1) is below 600 and have an aromatic series skeleton, and the weight-average molecular weight of described oxetane monomer (B2) is below 600 and have an aromatic series skeleton;
Solidifying agent (C), this solidifying agent are resol or have the aromatic series skeleton or the acid anhydrides of ester ring type skeleton, the hydrogenation thing of this acid anhydrides or the modifier of this acid anhydrides; With
Filler (D),
Wherein, in the total amount 100 weight % of all resins composition of the insulating trip that comprises above-mentioned polymkeric substance (A), above-mentioned monomer (B) and above-mentioned solidifying agent (C), the content of above-mentioned polymkeric substance (A) is in 20～60 weight % scopes, the content of above-mentioned monomer (B) is in 10～60 weight % scopes, and the total content of above-mentioned polymkeric substance (A) and above-mentioned monomer (B) is lower than 100 weight %
The glass transition temperature Tg of this insulating trip under its uncured state is below 25 ℃,
After insulating trip solidified, the breakdown voltage of the cured article of insulating trip was more than 30kV/mm.
2. insulating trip according to claim 1, wherein, described polymkeric substance (A) is a phenoxy resin.
3. insulating trip according to claim 2, wherein, the glass transition temperature Tg of described phenoxy resin is more than 95 ℃.
4. according to each described insulating trip in the claim 1～3, wherein, described solidifying agent (C) is:
Have the acid anhydrides of greasiness ring type skeleton, the hydrogenation thing of this acid anhydrides or the modifier of this acid anhydrides, perhaps,
The acid anhydrides that terpene compound and maleic anhydride obtain through addition reaction, the hydrogenation thing of this acid anhydrides or the modifier of this acid anhydrides with ester ring type skeleton.
5. insulating trip according to claim 4, wherein, described solidifying agent (C) is one of any represented acid anhydrides in following formula (1)～(3),
Figure FPA00001045404000011
Figure FPA00001045404000021
In the above-mentioned formula (3), R1 and R2 represent the alkyl or the hydroxyl of hydrogen, carbonatoms 1～5 respectively.
6. according to each described insulating trip in the claim 1～3, wherein, described solidifying agent (C) is for to have the resol of trimeric cyanamide skeleton or triazine skeleton or to have allylic resol.
7. according to each described insulating trip in the claim 1～6, wherein, described filler (D) contains the ball filler that median size is 0.1～0.5 μ m (D1), median size is the ball filler (D2) of 2～6 μ m and the ball filler (D3) that median size is 10～40 μ m
In the described filler (D) of 100 volume %, the content of described ball filler (D1) is in 5～30 volume % scopes, the content of described ball filler (D2) is in 20～60 volume % scopes, the content of described ball filler (D3) is in 20～60 volume % scopes, and the total content of described ball filler (D1), described ball filler (D2) and described ball filler (D3) is no more than 100 volume %.
8. according to each described insulating trip in the claim 1～6, wherein, described filler (D) is the filler (D4) through pulverize of median size below 12 μ m.
9. according to each described insulating trip in the claim 1～8, wherein, described filler (D) is for being selected from least a in aluminum oxide, boron nitride, aluminium nitride, silicon nitride, silicon carbide, zinc oxide and the magnesium oxide.
10. according to each described insulating trip in the claim 1～9, this insulating trip also contains dispersion agent (F), and described dispersion agent (F) has the functional group that comprises the hydrogen atom that can form hydrogen bond.
11. according to each described insulating trip in the claim 1～10, this insulating trip also contains rubber grain (E).
12. insulating trip according to claim 11, wherein, described rubber grain (E) is a silicone rubber particles.
13. according to each described insulating trip in the claim 1～12, wherein, in whole skeletons 100 weight % of described polymkeric substance (A), the content of aromatic series skeleton is in 30～80 weight % scopes.
14., wherein, have polycycle aromatic series skeleton in the main chain of described polymkeric substance (A) according to each described insulating trip in the claim 1～13.
15., do not contain woven fiber glass in this insulating trip according to each described insulating trip in the claim 1～14.
16. according to each described insulating trip in the claim 1～15, wherein, the insulating trip of its uncured state in the bending elastic modulus under 25 ℃ in 10～1000MPa scope, and after insulating trip solidifies, the cured article of insulating trip in the bending elastic modulus under 25 ℃ in 100～50000MPa scope;
The insulating trip that utilizes its uncured state that rotary-type Measurement of Dynamic Viscoelasticity device measures at the tan δ under 25 ℃ in 0.1～1.0 scope, and, when 25 ℃ were warming up to 250 ℃, the maximum value of the tan δ of insulating trip was in 1.0～5.0 scopes at the insulating trip that makes its uncured state.
17. according to each described insulating trip in the claim 1～16, its reactivity under its uncured state is below 10%.
18. a laminate structures, it comprises: thermal conductivity the heat conductor more than the 10W/mK, be laminated to the insulation layer on the one side at least of above-mentioned heat conductor and be laminated to above-mentioned insulation layer with lamination the opposite conductive layer on simultaneously of the face of above-mentioned heat conductor is arranged,
Wherein, described insulation layer is by making the insulation layer that each described insulating trip is solidified to form in the claim 1～17.
19. laminate structures according to claim 18, wherein, described heat conductor is a metal.
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